Oxyalkylated derivatives of certain intermediates obtained from certain carboxyl-containing xylenesoluble resins



Patented Oct. 16, 1951 OXYALKYLATED DERIVATIVES OF CERTAIN INTERMEDIATESOBTAINED FROM CER- TAIN CARBOXYL-CONTAINING XYLENE- SOLUBLE RESINSMelvin De Groote, University City, and Bernhard Keiser, Webster Groves,Mo.,

assignors to Petrolite Corporation, Ltd., Wilmington, Del., acorporation of Delaware No Drawing.

Original application February 21,

1950, Serial No. 145,579. Divided and this application August 30, 1950,Serial No. 182,165

The present application is concerned with hydrophile synthetic products;said hydrophile synthetic products being oxyalkylation products of theacylation product obtained by reacting (a) a fusible,carboxyl-containing, xylene-soluble, water-insoluble, acid-catalyzed,low-stage phenol-aldehyde resin; said resin being derived by reactionbetween a mixture of a difunctional monohydric hydrocarbon-substitutedphenol and salicylic acid on the one hand, and an aldehyde having notover 8 carbon atoms and reactive towards both components of the mixtureon the other hand, the amount of salicylic acid employed in relation tothe noncarboxylated phenol being suflicient to contribute at least onesalicylic acid radical per resin molecule; said resin being formed inthe substantial absence of trifunctional phenols, and said phenol beingof the formula in which is a hydrocarbon radical having at least 4 andnot more than 14 carbon atoms and substituted in the 2,4,6 position; and(b) an acylation-susceptible chemical compound in which the elements arecomposed exclusively of members selected from the class consisting ofcarbon, hydrogen, oxygen, nitrogen, and sulfur, and chlorine, with theproviso that the molecular weight of such second reactant shall not beover 25,000.

Attention is directed to our co-pending apformed in the substantialabsence of trifunc- 15 Claims. (Cl. 260-19) tional phenols, and saidphenol being 01' the formula in which R is a hydrocarbon radical havingat least 4 and not more than 14 carbon atoms and substituted in the2,4,6 position. See additionally our co-pending application, Serial No.8,722, filed February 6, 1948, now Patent 2,499,365, granted March '7,1950.

The carboxyl-containing xylene-soluble resin of the kind described canbe reacted with a variety of compounds reactive towards carboxylradicals, such as compounds having a hydroxyl radical, an amino radical,an amido radical, a sulfonamide or derivative thereof, or a combinationof such radicals or similarly reactive radicals. Such hydroxylatedcompounds may be composed of carbon, hydrogen and oxygen only or mayadditionally have some other element, such at nitrogen, sulfur,chlorine, etc. In fact, it is not necessary that oxygen be present, asin the case of an amine or ammonia. Stated another way, such carboxylmay be reactive towards any compound having either a hydroxyl or anamino or nitrogen atom, or both, or other obvious equivalents.

This broad invention is generic to at least three sub-genera. Onesub-genus is concerned with acylation-susceptible compounds derived froma carboxyl-containing resin'and a second reactant containing carbon,hydrogen and oxygen only.

A second sub-genus of the present invention is concerned with suchinstances where the acylation-susceptible compounds, either organic orinorganic, contain nitrogen. A third sub-genus of the broad invention isconcerned with certain products of acylationsusceptible organiccompounds in which there is present at least one element other thancarbon and hydrogen, and either oxygen or nitrogen, or both, said otherelement being selected from the class consisting of sulfur and chlorine.

The method of preparation of all the compounds within the generic classis essentially the same. The first step is to obtain and prepare afusible, carboxyl-containing, xylene-soluble, resin; and then react theresin with an acylationsusceptible compound of the kind previouslydescribed, and particularly an organic compound having a molecularweight under 25,000. The result of such acylation reaction, which may beesteriflcation or amidification, or both, is an acylation product orintermediate.

Having obtained such intermediate product by reaction with the carboxylradical of the xylenesoluble resin; the next step involves reaction withan alkylene oxide such as ethylene oxide, propylene oxide, butyleneoxide, glycide and methylglycide.

For all practical purposes such oxyalkylations are conducted in aconventional manner. The oxyalkylated derivatives so obtained areemployed for the resolution of petroleum emulsions of the water-in-oiltype. The oxyalkylated derivatives may be used for a variety ofpurposes, other than demulsiflcation, where surface-active materials areof value as. for example, producing emulsions, detergents, agriculturalsprays, further reaction with chemical compounds reactive towardshydroxyl radicals, etc.

Specifically, the use of such oxyalkylated derivatives is not limited tothe resolution of petroleum emulsions of the water-in-oil type.

The carboxyl-containing xylene-soluble resins which we use asintermediates for preparing the products of the present invention aredescribed in our application Serial No. 137,293, filed January 6, 1950,and reference is made to that application for a complete and fulldescription of these resins and to Examples 6a through 24a for speciflcexamples of suitable resins.

To produce the products of the present invention, these resins arereacted with acylationsusceptible materials reactive with the carboxylgroups present in the resin. In describing suit ableacylation-susceptible materials, to illustrate the invention, we willfirst describe acylation with suitable compounds containing only carbon,hydrogen and oxygen, then acylation with compounds containing nitrogen,then acylation with compounds containing chlorine or sulfur, and thendescribe the oxyalkylation of these intermediates to produce theoxyalkylated prodnets of the invention.

COMPOUNDS CONTAINING CARBON, HYDROGEN, AND OXYGEN ONLY The intermediatesare prepared by convenreactants containing carbon, hydrogen and oxygenonly. Where the reaction involves a hydroxyl radical free from otherinterfering radicals as in the case of a monohydric alcohol, polyhydricalcohol, fractional ester, or the like, one can employ any conventionalprocedure, but the one referred to is a customary esteriflcationreaction employing an acid catalyst. Other obvious equivalents suggestthemselves such as reaction with a polyhydric alcohol followed bysubsequent reaction with a high molal monocarboxy acid. There is nothingto be gained, however, by employing such added step.

For convenience, we have used a conventional two-piece laboratory resinpot. The cover part of the equipment had four openings: One for refluxcondenser; one for the stirring device; one for a separatory funnel orother means of adding reactants; and a thermometer well. In themanipulation employed. the separatory funnel insert for adding reactantswas not used. The device was equipped with a combination reflux andwater-trap apparatus so that the single piece of apparatus could be usedas either a re- 4 flux condenser or a water trap, depending on theposition of the three-way glass stopcock. This permitted convenient withwithdrawal from the water trap. The equipment, furthermore, permittedany setting of the valve without disconnecting the equipment. The resinpot was heated with a glass flber electrical heater constructed to fltsnugly around the resin pot. Sgeh heaters, with regulators, are readilyavaila le.

The selected resin, either dissolved in xylene or with xylene added, wasplaced in the resin pot along with the selected hydroxylated reactantand a small amount of catalyst, usually paratoluene sulfonic acid. Themixture was refluxed and stirred during the entire procedure.

When the phase-separating trap showed that the amount of water separatedwas approximately that expected from reaction the operation was stopped.The intermediate so obtained was, of course, dissolved in xylene. Thexylene was readily removable by vacuum distillation although forsubsequent reaction with an alkylene oxide there is no objection to itspresence.

The subsequent tables show the particular resin employed and the amount,the hydroxylated reactant and amount, the amount of catalyst employed(para-toluene suli'onic acid), added solvent and amount, the ratiobetween available hydroxyls and carboxyls, the approximate refluxtemperature, time of refluxing, the

tional acylation reactions employing carboxylamount of water evolved,and the appearance of containing xylene-soluble resins described inapthe final product. The data are in essence selfplication S. N.137,293, along with hydroxylated explanatory.

ARmt. tof Amt or A t r Ratio Reactant for Combinawe Carbox- Amt. of Acidm 0 Reflux Time, Water A ance of tion with Carboxyl g; lc Resin, Cata- 33 Temp., in out, S25 3: Free gj 'i Group Resin, Grams lyst, 0. hrs. c.c. Ester ployed, Grams Grams to By- Grams droxyl 1b Carbowax 4000 mono-418 74 as. 5 6 90. 1 1:1 170 4% 7.7 D k b r0 w n Wtn-disperslble earate.tacky Solid foam. Calibowax 4000 mono- 418 7a 85. 6 5 1:1 174 4% 104.....do

oea 3b ltl iylgieglyeolmono- 85.2 70 22s 5 160 1:1 168 4% 6.9 do Do.

oea 4b Emeglyeolmono- 89.3 7a 228 5 1:2 161 6% 9.8 -....do Do.

0. 5b Glyeerolmonooleata. 96.3 7a 223 5 197.7 1:2 153 5% 8.6 -....do....Do. 60 Diethylene glycol 101 7a 228 5 167 1:1 162 4 7.1 Dk brown soitWtr.-disperaible.

mono-ricinoleate. 1. 7b Glycerol mono-oleate 93 7a 228 5 152 1:1 161 47.8 Do. 80 Glyoeryi dioleaie 162 74 22s 5 1:1 162 4% 6.5 D k. brlownsltlyrilgaier disl0 1c. M OarbowaxlOOOmono- 392 10a 75 5 67.0 1:1174-182 6 10.4 wgi-disperslble steal-ate. foams.

Example number is that of 8. N. 187.298.

1 1 h m .m@ .m. .m di. mm b m mm an no M W m n m. 1 I I a t m m 1. mm M1.. 3 e... m m 1ooooo o mb o o s 0 0 1110 10 00. 6 In 1 n u .y .y 000000000000000 0 o 000 mm n MD D D D D D D 1 D D mD 1 mm D DDDDDDDDD@mDDDmDDDDDDDDDDDDnwmD D DDD m 1 W M 0%. w M mm. 5 mm. s s m m. T m v Il n q 1 m m m m m m m m m m m m m n n n m. n m m m n m n m m mm v m a hn n n n n m n n m m m m m u a m n u u u n r. .1. mm m .m m m m m m m m mn w m n n m m m m m n 0 b8 we ymmmmmmm mmmm W .nn b s o 0 O 0 o o 0 o op. mmhhh m njj mm 1 N A D T B n u u n n n D u n u m D D m m u u u n n un n u n n n u u r 0 0 4 3 7 8 5 2 3 6 8 7 9 0 6 no 0 r 96 t l I l u 1 ek 1224265 3 26152320800083324 2 0 9 2 6 MM 8 8 8 8 a 8 7 7 5 0 4 6 Au 43 mwaznmaamiil-mzu 0m lfilza-hiizomzfiflomnmd 5 5 5 7 6 VA Mu M M VA V AA M 4 M 4 44 444/44 444 4 4 mmm e 4 4 a a 5 a 5 e 5 s a a a W a MMmewwmwws m MWWWs wmm Mm4WWWmM s W M45 6 T X .1 2 7 6 8 M 5 w 5 w m w wm 2 1 9 52788 7 897 4 l 6 69 9 6 989 6 6 99 mmm H 1 1 1 1 1 1 1 1 1 1 mm m m m u mummnummm m umummmmmuwmmnmmmm n ummmm m mum m T n 1 U m 0M am2 2 MM 2 2 U .u 1 U 1 1 H 1 111 1111 .H 11111111111111111 1 11111 1 1111 td 1 0 IS 0 7 0 4 t mn Q 5 w 6 5 1 5 s c r 4 4 g m 4 m w 7 5 a 7 590254 2 1 21194503 5 27 9 25108 355 m 10 1 1 1 1 1 1 1 1 1 1 m m 1 m m unummmmmmn m mummmumnnxxmnmwnm m mum m 16m m 5 5 5 6 5 6 5 5 5 5 6 5 5556555555 5 55555555555555555 5 55555 5 565 5 7 m m z m m m m 2 m m x wu vnmmmmmmm m mmmmmummmmmmmummn m mmmmm m mmm a a a a a a a m m 1 m m 1m 1 m a m 1 a 1 1 Zmnmmmwmm .m .mnwwwmmammmmmmmmm .m mum. .m FM 11 080170705000208004 6 93144 8 B26 3 2 z o a 2 z s a 1 1 1 m m w m m m u ww m .m u m m 1. 5 a wmmmm mm m mwnmnmhg uwmnmwh 9 ame may a a a c e e ae 11 .1 u 1 1 1 .1 c .1 y y 0 n 0 e 0 0 mm mnmmmnnmw am w wmw mw"nn HUI"mm fi m w mw mo m d d d m 0 1.63? m em am v. e" n "111KB 5 u wf mi 0b 11I l l 1 I d -t m lt l 1x lt m m m m "x M nm c 0 nb m can. w w w w w w mmme wrl we eu m m" 0 d n n n n n.m.w.m.mce u h xx1 d h .c e 1e 1 1 8 h0. 9V. y 0 V. Cu v. v. v. v. v. v. m o m d 0% 0 d t o L m m m .a m.arrrrro .1 11.eh 110. h hm m n. c. m wawmmmnw m mnemnwmy h u A e n "e"w "e M333 m w mum m whm m 1 .1 .1 1 u e m m mmmmmmmw mnmmemdflwemmemdew dmmm o m .0 c c e c w d w. w mmv. v. M xm ananm meaeanynw 0m mce m whm n 1 .w mm h a a vlwnvwmu m c on ammmmm whtwfi tx mn mn wm wm wnwmmn m ummnwmmmmmmmmumu wm mw m1 111 o h h DoDoPov. v. medo 0. 0. o .w oe e .m m nm n n nrrrrr n r e1 t ...o1.av.t...mh mu wo m mmm m m mmdmmemhmnmmmmammammhumm m m .w wwmwwmwmwmwwwwwwm am wmmmmmmmmwm E E s o Lo o o o D D n GHRGHRHRHRHHHHHHP T DNMPD a 2 3m. m 10. w b w m o m w o ww b 1 b 1 1 1 b 1 N 1 1 1 1 1 1 1 1 1 m z a m 1 w m m mDwwmhhficmumhwmmm M Mwmmm m awe w ceptible compounds are prepared fromphenols havinga hydrocarbon substituent having from 4 to 14 carbon atomsin the 2,4,6 position and the aldehydes have 8 carbon atoms or less.These products are water-insoluble, xylene-soluble, fusible resins. Alarge number of them are .d'escribed in our Patent 2,499,365 and theiroxy- Example number is that of S. N. 137,293.

Other esters, useful as intermediates for the production of the productsof the invention, are

The alkyl phenol-aldehyde resins which are oxyalkylated to producesuitable acylation-susprepared from oxyalkylated derivatives of alkylphenol-aldehyde resins by reaction with the carboxyl-containingphenol-aldehyde resins.

alkylation to produce suitable acylation-susceptible products is alsodescribed in some detail in this patent. We refer specifically toExamples in, 3a, 5a, 7a and 8a of that patent for examples of suitablealkyl phenol-aldehyde resins, which on oxyalkylation giveacylation-susceptible compounds-suitable for the production of theintermediates here described.

In column 2 of the table the resins of column 2 designated by an arabicnumeral followed by a lower case 0" are the products of thecorresponding examples of Patent 2,499,365, while those designated by anarabic numeral followed by two lower case bs" are partially oxyalkylatedproducts identified under Ex. No." in the first column of the table.

Amt. Solvent Sod. Max Deriv- EtO Temp Taken Present Meth late TimePres., lbs. Solubilit in gy Gms.(Solom. dd ed, 8;? am.) t?" per sq.Water vent Free) (Xylene) Oms. inch in 1555 1445, 425 A 160 00Insoluble. 150 1167 848 1350 M 188 95 Emulsiflabla, 200 780 205 1050 M170 Water Soluble. 1a 518 482 16 1425 M 183 100 Emulsliiable. i as :2 a:2 :22 a: s a o. Gbb 768 177 800 M 161 100 Do. la 3g 23g l5 lzgg 95 B0.is 0. it? a: :2 as a :2 ela 4 0. 3a 1575 1425 50 400 150 80 Insoluble.1200 1510 1090 1225 M 158 80 Emulsiflable. 1300 1787 713 975 a 173 60Water Soluble. :22 a a a y a is s 1 s 0. 3a 280 533 10 1742 171 Do. 3a142 270 10 1778 M 150 no Do. 34 183 347 10 2445 M 205 D0. 34 208 396 101571 $4 160 75 Do. a i8 is a a e- 3e 0. 8 1580 1420 50 325 :2 150 50Insoluble. 2300 1490 1110 1000 i2 171 100 Emulsiiiable, 24b! 920 4101390 172 150 Soluble. 8a 736 664 25 1500 H 190 D0. 8a 490 440 15 1480 4160 150 Do.

The following examples illustrate and describe the oxyalkyl-atedderivatives of such phenol-aldehyde resins:

Example 11)!) The reaction vessel employed was a stainless steelautoclave with the usual devices for heating, heat control, stirrer,inlet, outlet, etc., which are conventional in this type of apparatus.The capacity was about 2 gallons. The stirrer was operated at a speed ofapproximately 250 R. P. M. There were charged into the autoclave 1555grams of a resin of the kind identified by- Example la of Patent2,499,365. This resin was dissolved in 1445 grams of solvent (xylene);45 grams of sodium methylate were added. The autoclave was sealed, sweptwith nitrogen gas, and stirring started immediately and heat applied.The temperature was allowedto rise to approximately -150 C. At thispoint the addition of ethylene oxide was started. It was addedcontinuously at such speed that it was absorbed by the reaction asrapidly as added. The amount of ethylene oxide added was 425 grams. Thetime required to add this ethylene oxide was one-half hour. During thisperiod of time the temperature was maintained at 145- C., using coolingwater through the inner coils when necessary and otherwise applying heatwhen necessary. The maximum pressure during the reaction was 60 poundsper square inch. The product obtained was water-insoluble.

This oxyalkylated product was further oxyalkylated in two successivesteps, resulting in the production of, first, an emulsifi-able productand, finally, of a readil water-disperslble or soluble" product. This isshown in the first 3 lines of the following table.

The other examples recited in the table represent still further examplesof the preparation of this oxyalkylated alkylphenol-aldehyde class ofreactants. That application includes a total ofsome68such examples.

Having prepared hydroxylated reactants as just described in Exampleslbb-27bb above, the carboxyl-containing resinous materials are thenreacted therewith to produce the acylation products which areintermediates useful for preparing products of this invention.

The acylation products obtained from such oxyalkylatedalkylphenol-aldehyde resins by reaction with a carboxyl-containingaldehyderesin are illustrated by the following table.

The column headed "Carboxylic reactant" shows by number thecarboxyl-containing resin employed in each example, such resins beingthose described under the same number and letter designationsapplication S. N. 137,293.

The polyhydric reactant designated 6350 in the following table is theresin of Example 3c of Patent 2,499,365 oxyethylated with 1750 grams ofethylene oxide-to 1760 grams of the resin with 2,000 grams of xylene assolvent, 40 grams 01 sodium methylate as catalyst, time one hour,maximum temperature 0., maximum pressure 100 lbs. per sq. in. It iswater soluble.

The polyhydric reactant designated "64220" in v the following table "isthe resin of Example 8a of Patent 2,499,365 oxyethylated with 1800 gramsof ethylene oxide to 1920 grams of resin with 2,000 grams of xylene assolvent, 46.5 grams of sodium methylate as catalyst, time 1% hours,maximum temperature 182 0., maximum pressure 105 lbs. per sq. in. It issoluble in water.

The polyhydric reactant designated 65b.," in the following table is aresin obtained following the procedure of Example la of Patent2,499,365, from technically pure nonyl phenol 660 grams, formaldehyde37% 243 grams, concentrated HCl 9 grams, monoalkyl (Cm-C20, principallyell-CH) benzene monosulionic acid sodium salt 2.5 grams, and xylene 300grams, which resin was oxyethylated with 1825 grams of ethylene oxide to1975 grams of resin, with 2,000 grams of xylene as solvent, 48 grams ofsodium methylate as 7 catalyst, time 1% hours, maximum temperature 9'181.5 C., maximum pressure 103 lbs. per sq. in. It is water soluble.

water formed is simply a fraction of a mole, that is, 3, 4, or 6 cc. Wehave found the figure Catalyst Amt Amt. Ex. No Ex. No. (Para- Used UsedSolvent Ratio Ex. No. gg g (SGlms. t fg ('sG ms. t (IEYIene) f ggg 2 3-gg Water out o ven o yen ms.

Reactsnt Free) Reactant Free) 61:11:)

63th 176 7a 107 337 7 1:1 150 to 170-- 4 Approx. theoretical 6300 141 7a171 354 7 2:1 150 to 170-- 4 Do. 63bb Y 70. 4 7a 128 359. 6 7 3:1 150 to1 4 Do. 03bb 176 9a 100 282 7 1:1 150 to 1 4 Do. 141 9a 159. 6 295. 4 72:1 150 to 170.. 4 Do. 6300 70. 5 9a 119. 7 302. 3 7 3:1 150 to 1 4 Do.6355 156. 5 1241 113. 5 312 7 1:1 150 to 1 4 Do. 6359 117 12a 170. 5312. 5 7 2:1 150 to 170 4 Do. 630!) 70. 5 1211 153. 5 262 7 8:1 150 to170 4 Do. 6317b 140.8 11a 112.6 297. 6 7 1:1 150 to 1 4 Do. 639!) 10811a 173 309 7 2:1 150 to 1 4 Do. 6309 70. 5 1111 168. 5 272 7 3:1 150 to170-. 4 Do. 6355 156. 5 8a 119. 5 311 7 1:1 150 to 17 4 Do. 6396 117 8a179. 5 314. 5 7 2:1 150 to 170 4 Do. 6395 70. 5 8a 161. 5 261. 8 7 3:1to 1 4 Do. 6400 157. 5 7a 101 294. 5 7 1. 2:1 150 to 170 4 Do. 6490131.5 741 171 328. 5 7 2. :1 150 to 170-. 4 D0. 6465 83 7a 161. 5 283. 57 3. 6:1 150 to 170 4 D0. .64bb 197 9a 100 320 7 1:1 150 to 170 4 Do.6405 157. 5 9a 159. 5 330 7 2:1 150 to 170 4 Do. 6455 105 9a 160 343 73:1 150 to 170 4 Do. 6495 175 12:1 113. 5 304. 5 7 1:1 150 to 170 4 Do.6455 131 1201 203 328 7 2:1 150 to 170 4 Do. 6499 87. 5 1211 170. 5 2757 3:1 150 to 170 4 Do. 65bb 181. 5 7a 95 285. 5 7 1:1 150 to 170 4 Do.65th 148. 5 7a 160 287 7 2:2 150 to 170 4 Do. 65b!) 109 7a 171 270 7 3:1150 to 170 4 Do. 6511b 234 9a 114 301 7 1:1 150 to 170 4 Do. 655!) 1639a 159. 5 247. 5 7 2:1 150 to 170 4 D0.

Still another class of esters are the esters deis not significant for anumber of reasons: (a)

rived from polyhydric alcohols and the carboxylcontainingphenol-aldehyde resins.

Example 94b The particular resin employed was the one described underthe heading of Example la of application S. N. 137,293. The polyhydricalcohol employed was ethylene glycol. The amount of ethylene glycol usedwas 9.3, grams. The amount of carboxylic resin was 256 grams. The amount01' para-toluene sulfonic acid was 5 grams. The amount of solvent(xylene) present was 292 grams. The reflux temperature varied from 150"C. to 170 C. The time of refluxing was 4 hours. The solvent-free productwas clear, reddish amber, and soft to tacky in appearance.

The water evolved was separated in a phaseseparating trap as previouslydescribed. In a large number of similar experiments we have takenparticular pains to measure the amount of water evolved. This, however,is not particularly significant, especially where the amount ofsometimes some of the water tends to hang up in the apparatus; (12)sometimes the reactants employed, although not necessarily in theinstant case, contain a trace of moisture or some other volatilesubstance which comes over with the water and the reading appears'to behigh; (0) sometimes some other reaction, such as etherification, takes.place. In this case the reaction was conducted until apparently no morewater due to an acylation reaction came over. We have indicated thisamount of water as being approximately theoretical which is inaccordance with results. The formation of the ester yields a producthaving diflerent physical characteristics, for instance, a highermolecular weight. It yields a product having difierent chemicalcharacteristics than the reaction mixture, for instance, asaponification number. Similarly, the acid value or hydroxyl value ofthe finished reaction mass is difierent from that of the unreactedinitial mixture.

The following table illustrates and describes this and other esterintermediates.

Amt. of Amt. of Ratio Reactant for Amt. oi

React- Carbox- Amt. of Acid 0! Car- Reflux Ex. Com bi net i o n SolventTime A earance of Solvent Free No. with Curboxyl $35 5 iga, @33 gffgfig(Xylene), gri 5 5?" m hrs. pp Ester Group Grams Grams Grams droxyl 494b.-- Ethylene glycol". 9. 3 7a 256 5 292 2:1 to 4 Cltear, reddishamber soft to 95b... Propylene glycoL. ll. 4 7a 256 5 292 2:1 C. to 4Clear, reddish amber suit to C. semi-fluid.

96b-.. Glycerol 13.8 7a 256 5 292 2:1 150 C. to 4 Clear, reddish ambersoft to 170 C. semi-pliable.

97b--- do 9.2 70 256 5 292 3:1 151509.650 4 Reddish,black, hard brittle.

98b." Diglycerol 44 7a 211 5 259 1:1 150 C. to 4 Reddish amber,semi-salt to 170 C. pliable.

9915 do 22 7a 213 5 261 2:1 150 C. to 4 Reddish black, hard and 170 Cbrittle.

1009 do 17. 6 7a 257. 4 5 294. 6 3:1 150 C. to 4 Reddish amber, hard and170 0. brittle.

1015.- Sorbitol 54. 6 7a 268 5 299 1.04:1 15509.0 to 4 Do.

1026 an 27.3 70 266 a aoo 2.08:1 1515 9 12) 4 Do.

1035.- .----do 1s 7a 256 s 292 3:1 9 1: 4 Do.

1045.- Tetramethylol 33 7a 256 5 292 2:1 150 0. to 4 Do.

cyclohexanol. 170

1050-. Propylene glycol" 304 7a 128 7 197 1:1 150 C. to 4 Dk. amberslightly opaque:

170 0. soft, fluid.

1 Example number is that 015. N. 137,293. Para toluene sultonic acid.

Further examples of acylation products which are included among theintermediates are products of high molecular weight obtained in variousways as, for example, the oxyethylation or oxypropylation of heat-stablecarbohydrates, including mannitan, sorbitol, etc. For example, sucrosecan be treated with an alkylene oxide (ethylene oxide or propyleneoxide) in a ratio of 100 moles of oxide for each initial hydroxylradical. Thus the molecular weight of such polyhydric alcohols may varyfrom ethylene glycol (62) to compounds whose molecular weights are inthe neighborhood of 25,000.

We prefer that the hydroxylated reactant, employed herein to esterifythe carboxyl-containing phenol-aldehyde resin, have a molecular weightnot exceeding 25,000.

COMPOUNDS CONTAINING NITROGIN These intermediates are those wherein theacylation-susceptible reactant contains nitrogen, and particularlynitrogen in connection with carbon and hydrogen, or carbon, hydrogen andoxygen, and are prepared by reaction with a nitrogen compound ofspecified character, as described below.

Nitrogen-containing compounds which are reactive towards the carboxylgroup can be divided into various classes as to their structure.Reactivity towards a carboxyl radical generally means the presence inthem of either an amino nitrogen atom or an alkanol radical or theequivalent, that is, hydrogen attached to oxygen. The inorganic nitrogencompounds include ammonia, hydrazine, etc. The organic nitrogencompounds include amines, such as primary, secondary and tertiaryamines, polyamines as well as monoamines, amines containing alkanolradicals or the equivalent, and amines which contain both a reactivehydrogen atom attached to oxygen and one or more reactive hydrogen atomsattached to nitrogen. For purposes of convenience thenitrogen-containing compounds employable as reactants here are dividedinto the following classes:

Class 1.Compounds containing only 1 nitrogen atom per molecule, with atleast 1 reactive hydrogen atom attached hereto, but in the absence ofreactive hydroxyl groups. Ammonia and hydrazine are examples ofinorganic compounds of this class. Primary amines like ethylamine,isopropylamine, butylamine, amylamine, hexylamine, heptylamine,octylamine, decylamine, tetradecylamine, hexadecylamine, andoctadecylamine are members of the class. High molal primary amines, likethose sold by Armour & Company, Chicago, as Armeens, usually with afigure designation showing the numbers of C atomsin the alkyl radical,e. g., Armeen 10, Armeen 12, "Armeen 16, etc., are included. So aresecondary amines like diethylamine, dipropylamine, dibutylamine,diamylamine, dihexylamine, dioctylamine, etc. Also included are aniline,cyclohexylamine, bis-(dimethylbutyl) -amine, 1-3-dimethylbutylamine, 2-amyl-4-methyl pentane. Amldes are also included in this class, but arecommonly not attractive for use here because of the difficulty ofsecuring satisfactory reaction to produce secondary amides. Other usefulamines of this class will be suggested by the above-recited list.

Class 2.-Compounds containing only 1 nitrogen atom per molecule, but inwhich a hydroxyl group is the only reactive and functional group, ashere employed. In this class are tertiary alkanolamines likediethylethanolamine, dimethylethanolamine, triethanolamine,diethylpropanolamine, methyldiethanolamlne, ethyldipropanolamine,phenyldiethanolamine, etc. The products obtained by reacting such amineswith alkylene oxides like ethylene oxide or propylene oxide are alsouseful, e. g., triethanolamine may be reacted with ethyleneor propyleneoxide. Alkyl primary amines, particularly those in which the alkvl grouporiginates in fatty materials and contains from about 10 to about 18carbon atoms, may be treated with such alkylene oxides to produce usefulnitrogen compounds of the generic formula, Rdi(A1kO) nH-N. Similarly,amides of the generic formula RCONHz, may be oxyalkylated to producecompounds of the generic formula,

)AlkOhH RC ON\ (AlkO) .H

The ricinoleyl amides of diallqrlamines are also examples of this class.Other examples of similarly useful reactants of this class will besuggested by the above list.

Class 3.-Compounds containing only 1 nitrogen atom per molecule andhaving, in addition to at least 1 reactive hydrogen atom attachedthereto, also at least 1 reactive hydroxyl group. In this classareincluded monoethanolamine, diethanolamine, monopropanolamine,dipropanolamine, ethylethanolamine, propylethanolamine,ethylpropanolamine, phenylethanolamine, 2-amino-Z-methyl l-propanol,4-amino-4-methyl-2- pentanol, 4-amino-2-butanoll-dimethylaminoz-propanol, 5-isopropylamino-1-pentanol, etc. Thehigh-molal monocarboxy acid amides or! monoalkanolamines are alsoexamples of this class. Obvious equivalents will be suggested by theabove list.

Class 4.Esters of tertiary alkanolamines having only 1 nitrogen atom permolecule, to which nitrogen atom there are attached no reactive hydrogenatoms, but in which ester molecule there is at least 1 reactive hydroxylradical, either attached to the nitrogen atom through a suitabledivalent radical or else as a part of the acyl radical present in saidester. The acyl radicals are those found in monocarboxy acids having 8 Catoms or more. Examples of this class of nitrogen compound are the esterproduced from oleic acid and ethyldiethanolamine or from ricinoleic acidand diethylethanolamine. In the case of the above oleic ester,esteriflcation consumes only one of the two hydroxyl groups originallypresent in that alkanolamine, leaving one such reactive hydroxyl groupin the ester, for use for the present purpose. In the case of thericinoleic ester above, esteriflcation consumes the only hydroxyl grouporiginally present in the alkanolamine there used; but the ricinoleicradical itself contains a reactive hydroxyl group, and the ester istherefore still reactive for the present purpose. In preparing thecompounds of this kind, there may be employed only as many acyl radicalsas there are alkanol radicals, less one; except that, if the acylradical itself retains at least one reactive hydroxyl group afteresterification, then one may use as many acyl radicals as there arealkanol radicals. Examples of suitable alkanolamines have already beenrecited under Class 2 above; but some of the examples there recited willnot serve here in all cases because they contain only one reactivehydroxyl group and this is destroyed in esterification. If ricinoleicacid is the acylating reactant, all those 13 recited there are usefulhere. It is apparent from the foregoing description that the intent isto retain at least one reactive hydroxyl group in the ester preparedfrom the tertiary alkanolamine and the acylating reactant employed.

Class 5.Compounds which are non-resinous,

which contain more than 1 nitrogen atom per molecule, and which containno acyl group. Examples include the alkylene polyamines likeethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, propylenediamine, dipropylenetriamine, etc.These alkylene polyamines may be treated with an alkylene oxide likeethylene oxide or propylene oxide to produce derivatives which are alsouseful here, such as hydroxyethylethylenediamine,tetraethanoltetraethylenepentamine, etc. Oxyalkylation may be continued,of course, until a considerable number of alkyleneoxy groups have beenintroduced, without adversely affecting the utility of such derivativeshere. Imidazolines, both mono-imidazolines and di-imidazolines, areincluded in this present class. Such compounds may be prepared byreacting, under sufliciently severe conditions, a monocarboxylated acidand an alkylenepolyamine. For example, when oleic acid andtetraethylenepentamine are reacted in molar proportions at a temperaturesomewhat exceeding 200 C. amidification first occurs, with theelimination of 1 mole of water. On continued heating, especially attemperatures approaching 300 C., a second molecule of water is splitout, the acyl group becomes an alkyl group, the imidazoline ring isformed, and the product is the monooleyl imidazoline oftetraethylenepentamine. If the proportion of fatty acid is doubled, adioleyl imidazoline is produced, instead. Examples of such monoanddi-imidazolines are recited and described in U. S. Patent Nos. 2,466,517and 2,468,163, dated April 5, 1949, and April 26, 1949, respectively, toBlair and Gross. Furthermore, U. S. Patent No. 2,369,818, dated February20, 1945, to- De Groote and Keiser, illustrates the fact that suchimidazolines may be subjected to reaction with an alkylene oxide likeethylene oxide, to produce oxyalkylated derivatives thereof which areuseful here.

Other examples of suitable reactants of the present class include3-diethylaminopropylamine, 1-3-diaminobutane, triglycoldiamine, and thecompound, NHz (CH2) (CH2) 6O (CH2) sNI-Iz. See also the co-pending caseof one of us, Serial N0. 107,381, filed July 28, 1949, for additionalexamples of suitable nitrogen compounds of this class.

Class 6.Compounds containing more than 1 basic nitrogen atom permolecule, and which also contain at least one high molal acyl group. Theamides produced from monocarboxy acids like the fatty acids and alkylenepolyamines like tetraethylenepentamine, and referred to in Class aboveas being intermediates formed in the preparation of certainimidazolines, are representative of this class. For example, if onereacts 1 mole of oleic acid with 1 mole of tetraethylenepentamine until1 mole of water of reaction is removed, the product is an amide of thepresent class. Stearic acid or tall oil or other detergent-forming acidhaving at least 8 C atoms may be substituted for oleic acid in producingsuch an amide, with equally satisfactory results. Other alkylenepolyamines such as ethylenediamine, diethylenetriamine,triethylenetetramine, etc., may be substituted fortetraethylenepentamine in the examples just discussed, to producedesirable amides. Or such polyamine may be oxyalkylated prior to use inthe amidification reaction, using ethylene oxide or propylene oxide. Ifimidazolines of the kind included in Class 5, immediately above, areacylated, such acylated imidazolines are then properly included in thepresent class of nitrogen compounds. Other useful examples of nitrogencompounds of the present class are described in U. S. Patent No.2,243,329, dated May 27, 1940, to DeGroote and Blair.

Of all the members of this sixth class of nitrogen compounds, we preferto employ as reactants here a type of product which is related to theesters of Class 4 above. If, instead 01 using molal proportions of highmolal monocarboxy acid having 8 carbon atoms of more and of tertiaryalkanolamine, as in the preparation of materials of Class 4, above, oneemploys 2 or more moles of alkanolamine for every mole of monocarboxyacid, desirable reactants of the present class are formed. These may betermed acylated polyaminoalcohols. To describe more precisely thisparticular and preferred type of Class 6 nitrogen compound, thefollowing statement is made:

The compounds are acylated derivatives of a basic polyaminoalcohol ofthe formula:

/RII H 0R"),.N

said acylated derivatives thereof being such that there is at least oneoccurrence of the radical RCO, which is the acyl radical of amonocarboxy detergent-forming acid having at least 8 and not more than32 carbon atoms; the amino nitrogen atom is basic; R" is a member of theclass consisting of aminoalkanol radicals, and polyaminoalkanolradicals, in which pclyaminoalkanol radicals the amino nitrogen atomsare united by divalent radicals selected from the class consisting ofalkvlene radicals, alkyleneoxyalkylene radicals, hydroxyalkyleneradicals, and hydroxyalkyleneoxyalkylene radicals, and all remainingamino nitrogen valences are satisfied by hydroxyalkyl radicals,includingthose in which the carbon atom chain is interrupted at leastonce by an oxygen atom; R. is an alkylene radical having at least 2 andnot more than 10 carbon atoms;

n is a small whole number varying from 1 to 10; I

and RC0 is a substituent for a hydroxyl hydrogen atom.

In the foregoing formula, R may, in some of its multiple occurrences inthe molecule, represent the same alkylene radical or it may representdifferent alkylene radicals, so long as each R contains from 2 to 10carbon atoms. For example, oxyethylated, oxypropylated triethanolaminewould contain some R radicals which are CaH4 radicals, and others whichare CaHv radicals.

Further description .of this acylated polyaminoalcohol reactant will befound, for example, in U. S. Patent No. 2,470,829, dated May 24, 1949,to Monson. As a specific example of this preferred class of nitrogencompound, a passage from said Morison patent will be recited laterbelow, in this application.

It is to be understood that isomeric forms of the nitrogenous compoundsof all 6 classes above may be employed instead of the forms referred toabove, without departing from the invention.

The acylation products which constitute the intermediates here describedare prepared by reacting a member of the class of carboxyl-con- 15xylene-soluble, water-insoluble, acidcatalyzed, low-stage,phenol-aldehyde resins with a member of one of the classeso! nitrogencompounds just recited above. In the more specific embodiment of thispart of our invention, or what might be called its sub-generic aspect,reaction is eil'ected between a resin of such class and a member of onegroup in Class 8 of said classes of nitrogen compounds. Both aspects areconsidered below.

Although the reactions involved here may be ammonolysis, esteriilcation,or amiditication reactions, they all involve the introduction, into thenitrogen compound, of an organic acyl radical; hence the reactions areall properly termed acylation reactions, and the products are acylationproducts.

The following examples will illustrate this acylation reaction andpreparation of such acylated intermediates.

For convenience, we have used a conventional two-piece laboratory resinpot. The cover part of the equipment had four openings: One for refluxcondenser; one for stirring device; one for a separatory tunnel or othermeans for adding reactants; and a thermometer well. In the manipulationemployed, the separatory funnel insert for adding reactants was notused. The device was equipped with a combination reflux and water-tapapparatus so that the single .piece of apparatus could be used as eithera reflux condenser or a water trap, depending on the position of thethree-way glass stopcock. This permitted convenient withdrawal of waterfrom the water trap. The equipment, furthermore, permitted any settingof the valve without disconnecting the equipment. The resin pot washeated with a glass fiber electrical heater constructed to fit snuglyaround the resin pot. Such heaters, with regulators, are readilyavailable.

The selected carboxyl-containing resin, either dissolved in xylene orwith xylene added, was placed in the resin pot, along with theappropriate other reactant. In the event that the other reactant wasnon-basic, such as a hydroxylated amide, a small amount of catalyst,usually paratoluene. sulfonic acid, was added. When the other reactantwas basic, as in the case of triethanolamine, usually no catalyst wasadded.

The mixture was refluxed and stirred during the entire procedure.

When the phase-separating trap showed that theamount of water separatedwas approximately that expected from the reaction, the operation wasstopped. The intermediate so obtained was, of course, dissolved inxylene. The xylene was readily removable by vacuum distillation althoughfor subsequent reaction with an alkylene oxide there is no objection toits presence. The following examples illustrate the process:

Example 1060 The carboxyl-containing resin oi. Example of application 8.N. 137,293, in which the ratio or amyl phenol to salicylic acid in theoriginal reaction mass was 4:1, was mixed (228 grams) with 38.9 grams ofcommercial triethanolamine and 222 grams of xylene. In this mixture theratio of COOH radical to amine was 1:1. A catalyst, para-toluenesultonic acid (5 grams), was added and the mass was refluxed atappromixately 145' C., in a conventional glass laboratory resin potassembly, just described. After approximately 7 hours, the theoreticalvolume of water had been collected and the operation was stopped. Theproduct, which was a dark-brown, brittle solid, somewhatwater-dispersible, was the ester of the carboxyl-containing resin.

In similar fashion, several carboxyl-containing =resins of the kindabove described were reacted with nitrogen compounds of the variousclasses just recited, to produce the desired acylation products orintermediates. These examples are not set out here in the detailaccorded Example 106b above; but are condensed into the following table.It is to be understood that the procedure is in general that 0! Example106b. Details of each of such preparations, including the nature of theresin and the nitrogen body employed, the amount of each, the amount ofxylene present, the amount 01' catalyst (paratoluene sulfonic acid)employed, if any, the molal ratio 0! carboxyl radical, COOH, to nitrogenbody, the temperature of the reaction mass during processing, the timeof processing, the amount of water evolved, are all set out in thetable. The product was in all cases a dark-brown, brittle solid. In allinstances except in Example b, it was water-dispersible.

Resin Ratio Ex Amt. Amt. X iene Catalyst Temp, Time, Water No EL (g.) N(g.) g. (g.) g gg 0 Hrs. Out

1060. 7a 228 Triethanolamine 3B. 9 222 5 1 :1 7 Theory 1070. 7a 228Diethanolsmine 27. 4 222 5 1:1 147 7 Do, 1M0. 7a 228 Dipropanolamme. 34.7 22 5 1:1 152 7 D0. 1000. 94 Z10 Diethylenetriamine 25. 2 200 1:1 145 7Do. 1100.. 9a 200 Armoen 10 45.3 200 1:1 5 D0. 1110.. 9a 110 Armeen 124i46.8 I!) 1:1 150 6 D0. 1120.. 9a 230 Armeen l6d. 61.7 200 1:1 150 5 Do.1130.. 9a 200 Armeen HTD 56. 6 200 1:1 150 6 Do. 1140.. 9a 200 Armeen18D 67. 6 IX) 1:1 150 5 Do. 1150.. 0a 200 Armeen CD (Coco 50.5 200 1:1150 5 Do. 1160.. 9a 200 Isopropanolamine l8. 4 200 1:1 145 5 Do. 1170..9a 200 H droxyethyl-ethylenediamine 25. 5 200 1:1 147 6 Do. 1180.. 9a200 D propyienetriamine 32. 1 200 1:1 147 5 Do. 1190 9a 2002-amlno-2-rnethyI-Lpropanol 21. 8 200 l :1 149 5 Do. 117:. 9a 210Diethanolamine 25. 8 2D 1: 1 152 5 Do. 1210.- 9a 200 Armeon TC 107 2001:1 152 6 Do. 122). 9a 200 Armeen 2H1 128 200 1:1 162 6 Do. 1230. 0a 200Di-n-butylamine 31. 8 200 1:1 147 6 Do. 1240. 9a 200z-amino-emethyl-pentane. 24. 7 200 1 :1 145 6 Do. 1250. 9a 200n-Decylamine 38. 5 200 1:1 145 5 Do. 1260. 7a 428 Dime-thyiethanolamine.44. 5 303 1:1 150 8 Do. 1270.. 9a 450 d 50 31] 1:1 150 8 Do. 18'. 9a 26930. 6 291 1:1 8 Do. 1290.. 8a 291 30.2 178 1:1 150 8 Do. 1300- 111: 28330. 8 286 1:1 150 8 Do.

1 Example number is that of S. N. 137,203.

Non: The "Armoens" are high molal primary amines Armour t 00., Chicago.See their catalog entitled "Arm pre in most cases from fatty materialsand are an lied commorciaii b Ioriurther description 0! them. pp 7 y 17Example 131 b One mole of tetraethylenepentamine was oxyalkylated withethylene oxide until 7 moles thereof had been absorbed, using theconventional procedure described above. This operation consumed 20minutes, at a temperature of 165 C. and maximum pressure of 70 p. s. i.

This product was then esterified with 1 mole of ricinoleic acid, usingno catalyst and continuing heating at 240-250 C., for 1.5 hours,distilling oil? 1 mole of water oi. esterification, in that time. Thisesterification product was then acylated by reacting it with acarboxyl-containing. phenolaldehyde resin, as follows: Use 177 grams ofthe just-prepared acylation product and 189 grams of the resin ofExample 7a of application S. N. 137,293, plus 234 grams of xylene. Nocatalyst was required. The reaction mass was refiuxed with stirring fora total of 8 hours, the temperature being 150 C., during which time atheoretical amount of water was distilled off. The xylene-free productwas a dark-brown, brittle solid.

Example 1321;

One-half mole of triethylenetetramine and 0.5 mol. of tall oil wasreacted to produce an amide, the reaction being conducted over a time of7 hours, with the temperature at 200 C. for 5.5 hours, and finally at240 C. for 1.5 hours. A total of 9 ml. of water was distilled off andcollected in this time. The amide so produced was reacted with the resinof Example 7a of application S. N. 137,293, using 140 grams of amide,265 grams of resin, 288 grams xylene, no catalyst. The temperature washeld at 150 for 8 hours of heating, stirring, and refluxing, the waterof reaction being distilled oil. The resulting acylation product was adark-brown, brittle solid.

Example 1335 An amide was prepared from tall oil andtetraethylenepentamine, using 0.5 mol. of each reactant. After heating 2hours at 240 0., about 10 ml. of water had distilled. The amide wasacylated using the carboxyl-containing resin of Example 9a ofapplication S. N. 137,293. To do this, use 132 grams of the amide justprepared, 214 grams of the carboxyl-containing .resin, 373 grams xylene,no catalyst. The temperature was 150 C. during heating and stirring withrefiuxing, which proceeded over 8 hours time. Water of reaction wasdistilled, leaving a xylene solution of the desired acylation product.Said product, in absence of the solvent, was a redbrown, brittle solid.

Example 134D Prepare the mono-ester of tall oil and triethanolamine byheating 1 mole of each for 240-250 C. for 1.5 hours. Mix .125 grams ofsaid ester, 219 grams of the carboxyl-containing phenolaldehyde resin ofExample 9a of application S. N. 137,293,- and 255 grams xylene in theconventional resin pot, adding no catalyst. Reflux with stirring, at 150C., for 8 hours, distiling ofi the water of reaction.- The resultingacylation product, xylene-free, is a red-brown, brittle solid.

Example 135D Prepare the reaction product of ricinoleic acid anddiethylethanolamine by employing molal proportions of these reactants,and heating at 240-250 C. for 1.5 hours. The resulting product stillretains the OH group in the ricinoleic acid residue present. React thisproduct with the carboxyl-containing phenol-aldehyde resin of Example 9aof application S. N. 137,293 by refluxing, with stirring, 117 grams ofthe amine product, 224 grams of the resin, 259 grams xylene, without acatalyst, for 8 hours, distilling ofi the water of reaction. Theproduct, xylene-free. is a redbrown, brittle solid.

Example 136D Prepare an oxyethylated product from triethanolamine byintroducing 3 moles of ethylene oxide per mole of triethanolamine, in aconventional oxyalkylation procedure, already described, no catalystbeing required. Time required was 15 minutes; maximum temperature, C...

maximum pressure 60 p. s. i. The oxyalkylated triethanolamine, 85.5grams, is mixed with the carboxyl-containing phenol-aldehyde resin ofExample 9a of application S. N. 137,293, 242 grams, and xylene, 272grams, no catalyst being added. Stir andreflux at 150 C. for 8 hours,distilling oil? the water of reaction. The xylene-free product is ared-brown, brittle solid.

Example 137b Example 1385 Oxyalkylate 1 mole of triethanolamine, using3.46 moles of propylene oxide as in Example 32b above, the reactionrequiring 8 hours at a maximum temperature of C. and a maximum pressureof 200 p. s. i., and subsequently introducing 2.97 moles ethylene oxideinto said oxypropylated amine, in 30 minutes, maximum temperature 160C., maximum pressure p. s. i. Thereafter, react the oxyalkylated amine,130 grams, with the carboxyl-containing phenol-aldehyde resin of Example9a of application S. N. 137,293, 216 grams, xylene, 254 grams, but nocatalyst. Stir and reflux 8 hours at 150 C., distilling ofi the water ofreaction. The product, solvent-free, is a red-brown, brittle solid.

Example 13% React 0.5 mole of stearic acid and 0.5 mole oftetraethylenepentamine for 4.75 hours at 240 C., recovering 9 ml. waterin the operation. React grams of the amino product with 426 grams of thecarboxyl-containing phenol-aldehyde resin of Example 12a of applicationS. N. 137,293,adding 474 grams xylene, but no catalyst to the mixture.Stir and reflux 8 hours, distilling ofi the water of reaction. Thesolvent-free product is a dark-brown, brittle solid.

In preparing acylation product intermediates from a nitrogen bodyselected from Classes 1 to 6 above, and a carboxyl-containingphenol-aldehyde resin, we prefer to employ a nitrogen body selected fromthat sub-group of Class 6 which are acylated derivatives of basicpolyaminoalcohols.

This particular sub-group of nitrogen com- 19 pounds which are includedinthe above-described Class 6 are esters of tertiary alkanolamineshaving more than 1 nitrogen atom per molecule. They have also at least 1acyl group per molecule said acyl group being a higher molal group,-

having at least 8 C atoms. Their molecule contains at least 1 reactivehydroxyl radical, either having from 8 to 32 carbon atoms, or itsglyceride or other ester, and a tertiary alkanolamine. For example,oleic acid and triethanolamine react to produce a very desirable exampleof the present class of nitrogen body. In such reaction, there must bepresent at least 2 moles of the tertiary alkanolamine for acyl radicalpresent, else the product is at least in part a mono-amine of Class 4,as above stated. Usually, the acyl-containing reactant used to preparethe present acylated polyaminoalcohol does not itself contain a hydroxylgroup. In such cases, reaction must be effected between suchnon-hydroxylated-acylcontaining reactant and a tertiary alkanolaminecontaining at least 2 reactive hydroxyl groups; so that, after formationof the ester there will remain at least 1 reactive hydroxyl group toaccomplish reaction with the carboxyl-contain ing resin and to producethe acylated intermediate from which our final oxyalkylated product isto be derived.

To illustrate this: If ethyldiethanolamine is etherized by heating to atemperature sufliciently high to drive off a mole of water from 2 molesof the amine, the resulting polyamine contains 2 reactive hydroxylgroups, the other two having been destroyed in the etherization process.If one of the remaining two hydroxyl groups is esterified with oleicacid, there remains in the final product one CH group suitable forcombination with the COOH group of the carboxylcontaining resinreactant. Such an acylated polyaminoalcohol therefore qualifies here.

However, if etherization had been effected between one mole ofethyldiethanolamine and one mole of diethylethanolamine, two of thethree OH groups originally present would have been consumed. The thirdOH group would be consumed in the esterification of the oleic acid; andthere would have been no residual OH group or groups available forreaction with the carboxyl-containing resin reactant. In such case, useof ricinoleic acid instead of oleic acid would have resulted in anacceptable final polyamino product, since the acyl group of ricinoleicacid itself contains a reactive hydroxyl group and this would have beenavailable for reaction of the acylated polyaminoalcohol with thecarboxyl-containing resin.

Therefore, in preparing acylated polyaminoalcohols of the desired class,one must bear in mind that such product must in all cases retain atleast one OH group capable of reacting with the COOH group of thecarboxyl-containing resin. In other words, if the basicpolyaminoalcohol, before acylation, be represented by the formulawherein R is usually selected from the class of ethylene, propylene,butylene, hydroxypropylenc, and hydroxybutylene radicals, and R" is, inat least one instance, a nitrogen-containing radical, then at least oneR" radical must contain an OH group, so that there are present in saidpolyaminoalcohol, before its acylation, at least 2 reactive OH groups;and, after acylation, it will still retain at least one OH group.Different occurrences of R in a single molecule may, of course,represent different alkylene radicals or they may represent the samealkylene radical.

Oxyalkylation of the alkylene polyamines, to introduce OH groupsthereinto, produces polyaminoalcohols suitable for acylation here. Asabove stated, such oxyalkylated alkylene polyamines must contain aminimum of two OH groups before acylation with the high molaldetergent-forming monocarboxy acid or equivalent, so that aminirnum ofone OH is found in the finally prepared acylated nitrogen body; unlesssaid detergent-forming acids acyl group itself contains one or more OHgroups, as in the case of ricinoleic acid, hydroxy-stearic acid,dihydroxystearic acid, etc.

The preparation of suitable acylated polyaminoalcohols in not novelwith'us here. It has been disclosed in numerous patents, including thefollowing: U. S. Patents Nos. 2,324,488 and 2,324,490, both dated July20, 1943, to DeGroote and Keiser; 2,259,704, dated October 21, 1941, toMorison and Anderson; 2,306,329, dated December 22, 1942, to DeGroote,Keiser and Blair.

Examples of the preparation of acylated polyaminoalcohols include thefollowing:

One mole of ricinoleic acid is heated with 3 moles of triethanolamine atapproximately 250 C. for 6 hours. The product is an acylatedpolyaminoalcohol.

One mole of castor oil is substituted for ricinoleic acid and 9 moles oftriethanolamine are employed instead of 3, above. The product closelyresembles that of the first example above.

Oleic acid may be substituted for ricinoleic acid or castor. oil. Talloil, which is principally a mixture of oleic and rosin acids. may besubstituted for the fatty acids. Different proportions oftriethanolamine may be used, so long as at least 2 moles oftriethanolamine are present for every acyl radical present.

As a, preferred procedure for preparing an acylated polyaminoalcohol forthe present purpose, the following is given, substantially as it appearsin U. S. Patent 2,470,829, dated May 24, 1949, to Monson:

A mixture of diamino and triamino materials is prepared, (by heatingtriethanolamine) which correspond essentially to the two following typeforms:

CzHrCH CZHAOH OHCZHI NC2H4O CzHiN OHCzH After determining the averagemolecular weight of such mixture, it is combined with castor oil in theproportion of 1 pound mole of castor oil for 3 pound moles of the mixedamines, pound mole" in the latter case being calculated on the averagemolecular weight, as determined. Such mixture is heated to approximately-260 C.

for approximately 6 to hours. until reaction is complete, as indicatedby the disappearance of all of the triricinoleln present in the castoroil.

Example 140!) Prepare a polyamino product from 925 grams of castor oiland 1090 grams triethanolamine, by heating at least 2 hours at atemperature of 250 C., and preferably 6 hours or even longer. Theproduct contains approximately 2.5 triethanolamine residues perricinoleic residue. Use 137 grams of it, 213 grams of thecarboxyl-containing phenol-aldehyde resin of Example 19a of appli-'cation S. N. 137,293, and 250 grams xylene, but no catalyst, to producean acylation product of said amino material. Reaction is conducted bystirring with reflux for 8 hours at 150 C. and distilling off the waterof reaction. The product is a dark-brown, brittle solid.

Example 1 41 b Produce a derivative of triethanolamine by reacting 885grams soybean oil with 1090 grams triethanolamine for 6 hours at 250 C.React 137 grams of the product with 209 grams of the carboxyi containingphenol-aldehyde resin of Example 20a of application S. N. 137,293,adding 254 grams xylene but no catalyst in the reaction. Reflux and stir8 hours at 150 C., distilling off the water of reaction. The product,when solvent-free, is a dark-brown, brittle solid.

Example 142i:

React 900 grams of tall oil with 2,180 grams of triethanolamine for 6hours at 250 C. Thereafter mix 140 grams of this product with 112 gramsof the carboxyl-containing phenol-aldehyde resin of Example 911 ofapplication S. N. 137,293, and 348 grams xylene, but no catalyst. Refluxthe mixture, with stirring, for 8 hours, distilling oil the water ofreaction. The product was not freed of solvent; but was used in xylenesolution in the preparation of oxyallwlated derivatives, as noted below.4

In the preparation of acylated intermediates from nitrogen-containingacylation-susceptible reactants and carboxyl-containing phenol-aldehyderesins we prefer that said nitrogenous COMPOUNDS CONTAINING Cnnoxmr: onSULFUR These intermediates are those in which a carboxyl-containingpheno-aldehyde resin is reacted with an organic acylation-susceptiblereactant which contains chlorine or sulfur atoms or both in itsmolecule. In addition to carbon and hydrogen, oxygen or nitrogen, orboth, may be present in such reactant.

Examples of chlorine-containing acylationsusceptible reactants usablehere include chlorinated lower glycerides, like dichloromonostearin ordichlorodistearin, produced by the chlorination of oleic acid to formdichlorostearic acid, and the subsequent reaction thereof with an excessof glycerol. If desired, the dichlorostearic acid may be esterified inmolar proportions with a polyhydric alcohol to produce a fractionalester containing chlorine; or such halogenated acid may be reacted withan alkylene oxide like ethylene oxide to produce such a fractionalester.

Cardanol is a substituted phenol derived from cashew nutshell oil, andcontains an ethylenic side chain having 14 carbon atoms or more. It maybe subjected to mild chlorination, to introsee U. 5. Patent No.2,368,709, dated February 6, 1945, to Harvey. To produce a suitableacylation-susceptible reactant from such chlorinated cardanol, one maysubject it to oxyalkylation; or one may form a phenol-aldehyde resinfrom said chlorinated cardanol and an aldehyde like formaldehyde, andsubsequently oxyalkylate said resin. Either oxyalkylated derivative isusable here. See our co-pending application, Serial No. 8,722, filedFebruary 16, 1948, now Patent 2,499,365, granted March 7, 1950, whereExample 258a relates to the production of a resin from cardanol andformaldehyde and Example 17b describes production of the oxyethylatedderivative thereof. The same procedure may be employed to produce asimilar resin fromchlorinated cardanol and formaldehyde, and theoxyalkylated derivative thereof, respectively.

A chlorinated phenol, like para-chlorophenol, may be oxyalkylated toproduce a chlorine-containing, acylation-susceptible product which isusable as a reactant here. If desired, p-chlorophenol, for example, maybe converted into a resin by reaction with an aldehyde, and saidchlorine-containing phenol-aldehyde resin may be oxyalkylated to producea reactant suitable for the present purpose. See Example 203a of ourco-pending application, Serial No. 8,722, filed February 16, 1948, fordetails for preparing such a resin.

Epichlorohydrin is a useful tool for introducing the chlorine atom intomolecules which originally contain a reactive hydrogen atom or otherreactive element capable of reacting with such epichlorohydrin. Suchreactions are well-known and are not described here.

Where an alkylene oxide like ethylene oxide is employed to produce anacylation-susceptible derivative of a chlorine-containing material, itis often desirable to employ stannic chloride as a catalystin thereaction, rather than the otherwise more commonly employed alkalinecatalysts, like caustic soda. The reason is that such alkaline catalyststend to de-chlorinate the halogenated reactant under the conditionswhich maintain during oxyalkylation, and this eliminates or destroys thecatalyst. 1

Ethylene chlorohydrin and glycerin chlorohydrin are additional examplesof usable chlorine containing adylation susceptible reactants.

Sulfur-containing acylation-susceptible materials include Vultac, a lineof resinous products of Sharples Chemicals, Inc., Philadelphia. This isthe trade-mark of a number of sulfurcontaining resinous materials,stated by the manufacturer to have the following generic structuralformula:

on OH n on 3-s.-E EHQPE I R R R and to contain diifering amounts ofsulfur. These products, alkylphenol sulfides, may be reacted withalkylene oxides, like ethylene oxide, to produce acylation-susceptiblederivatives which are useful here. If desired, they may be reacted witha suitable aldehyde, like formaldehyde, to form resins; and such resinsmay in turn be oxyalkylated as before, to produce acceptableacylation-susceptible derivatives. See Example 346a of our co-pendingapplication, Serial No.

duce chlorine into such unsaturated side chain. 76 8,72 filed February6. 1948. wherein Vultac resins are referred to; and to Example 64b ofsaid co-pending application, wherein the oxyethylation of such Vultacresin is recited.

Santolite MS is the trademark of a sulfonamideformaldehyde resinmanufactured by Monsanto Chemical Company, St. Louis. Suchsulfur-containing material is referred to in Example 363a of ourco-pending application, Serial No. 8,722, filed February 16, 1943; andits oxyethylation is described in Example 77b of said co-pendingapplication. The oxyalkylated derivatives of said Santolite MS areusable acyla tion-susceptible reactants here. The Santolite MS, beforeoxyalkylation, is not particularly suitable for the present purpose,because of the relative inactivity of the NH-- group.

Other examples of acceptable sulfur-containing reactants of the presenttype are to be found in U. S. Patent No. 2,353,694, dated July 18, 1944,to De Groote and Keiser; and in U. S. Patent No. 2,345,121, dated March28, 1944, to Hentrich and Kirstahler. Thiourea-formaldehyde resins maybe oxyalltylated; and such oxyalkylated derivatives may be employed forthe present purpose.

Sharples Chemicals, Inc., Philadelphia, also offers a polyethyleneglycoltertiary-dodecyl thicether under the trademark Nonic 218 which is anacceptable sulfur-containing reactant of the present type, and which ismade from dodecyl thioether by oxyethylation. Other oxyalkylatedmercaptans immediately come to mind as obvious equivalents of suchproduct, for the present use.

It is to be understood that the acylationsusceptible reactant maycontain both sulfur and chlorine in its molecule, just as the reactantderived from Santolite MS above contains both sulfur and nitrogen. Forexample, one may employ, instead of the Sharples Vultac resin above, thechlorinated derivative thereof. Alter- --natively, one may prepare anoxyalkylated deriva tive of said Vultac resin, as in Example 146!) justbelow; and then introduce chlorine into the molecule by reacting it withepichlorohydrin.

To produce, from a member of the foregoing class of chlorineorsulfur-containing, acylationsusceptible reactants, an acylation productsuitable for use as an intermediate in further reactions, it is onlynecessary to conduct a conventional reaction, such as an esterificationreaction-or, in case the chlorineor sulfur-containing reactant werewithout reactive hydroxyl groups, but were, for example, an amide orsulfonamide, an amidification reaction-between such reactant and acarboxyl-containing phenolaldehyde resin. To illustrate such reactions,the following examples are given.

Example 143!) Oxyethylated p-chlorophenol is prepared by reacting thephenol, 128 grams, with ethylene oxide, 88 grams, in an autoclave of thekind fully described above, at a temperature of approximately 170 C.,using 100 grams of xylene as a solvent, and 2 grams of stannic chlorideto catalyze the reaction. Oxyethylation is readily achieved in a 109grams of oxyethylated phenol so prepared, 425 grams of theamylphenolsalicylic acidformaldehyde resin of said Example 7:: and 300grams more of xylene for 4 hours in the presence of 2 grams para-toluenesulfonic acid, and distilling off water of esteriflcation. Approximatelythe theoretical quantity, 0.5 mole, of water was so recovered. Theproduct is a chlorine-containing acylation product or intermediate,usable for the preparation of oxyalkylated derivatives thereof for thepresent purpose.

Example 1441) Instead of oxyalkylating p-chlorophenol as in Example 14%just above, prepare a phenol-aldehyde resin from 128 grams of the phenoland 81 grams of 37% formaldehyde, employing the conventionalresinification procedure described in detail in application Serial No.137,293. Such resin, as prepared. contained grams of xylene added beforeresinification; and also 1 or 2 grams of concentrated HCl and ofalkylated aromatic sulfonic acid sodium salt employed to promote theresinification reaction. These are not removed from the mass beforeproceeding to the oxyethylation step. This is conducted by transferringto the autoclave, described above, approximately 137 grams of resin, 100grams of xylene, 2 grams of resinification catalyst, plus 2 grams ofstannic chloride (for oxyethylation catalyst). Ethylene oxide, 88 grams,is then introduced into this resin solution, maximum temperature beingabout 165 C., and absorption of "the ethylene oxide being accomplishedin 15 minutes. Approximately 225 grams of the oxyethylatedchlorophenol-formaldehyde resin so prepared, in solution in 100 gramsxylene, was added to 840 grams of the butylphenol-salicylicacid-formaldehyde resin of Example 9a of application S. N. 137,293, and300 grams more xylene were added. The mixture was placed in aconventional glass resin pot, already described,

and refluxed with stirring for 5 hours, in the presence of 3 gramsp-toluene sulfonic acid. At the end of this time 18 grams of water ofreaction, approximately theoretical in amount, had distilled off. Theproduct was a chlorine-containing, acylation product intermediate.

Example b Cardanol is chlorinated using the procedure recited in Example5 of U. S. Patent No. 2,368,709, dated February 6, 1945, to Harvey,until approximately 2 moles of chlorine have been absorbed by each moleof cardanol. The chlorinated cardanol, 500 grams, was mixed with 113grams 37% formaldehyde, 400 grams xylene, 3 grams concentrated HCl, and1.5 grams alkylated aromatic sulfonic acid sodium salt, in a glass resinpot, and refluxed 3.5 hours, after which water of reaction was distilledoff, the volume being about 25 ml.

A portion of the xylene solution of the resin so formed, adjusted tocontain 50% xylene solvent, was introduced into the autoclave alreadydescribed, a total of 820 grams of such solution containing 410 grams ofresin, being used; and 5 grams of stannic chloride were added ascatalyst. Subsequently, ethylene oxide, 585 grams, was added in sixportions, each of the first five being 90 grams, and the sixth, 135grams. The additions were absorbed quite readily, the temperaturesusually staying below about C., and addition being achieved in a matterof about 30 minutes in each case. The product is a chlorine-containingacylation-susceptible reactant. usable here.-

The oxyethylated resin, so produced from chlorinatedcardanol-formaldehyde resin, was reacted with the carboxyl-containingphenol-aldehyde resin of Example 7a. of application S. N. 137,293. .Intoa glass resin pot were introduced .350 grams of the cardanol derivativeand 395 grams of the butylphenol-salicylic acid-formaldehyde resin, 7grams p-toluene sulfonic acid, and 500 grams xylene. After stirring withreflux for 6 hours, water of reaction was distilled, its volume beingabout 18 ml. The product is a chlorinecontaining acylation product.

Example 146!) Vultac resin, a product manufactured by SharplesChemicals, Inc., Philadelphia, and consisting of an alkyl-phenolsulfide, as above described, 2,000 grams, was introduced into theautoclave previously described. To it were added 40 grams of sodiummeihylate and 2,000 grams xylene. Ethylene oxide, 4,000 grams, wasintroduced into the autoclave in four lots of 1,000 grams each. The timerequired for absorption of the first lot was 14 hours, at 160 C. The second lot was absorbed in the same time. The third lot was absorbed inhours, at 162 C.; and the fourth lot was absorbed in 4 hours, at 150 C.The product was a sulfur-containing acylation-susceptible reactant,usable here.

It wa reacted with the carboxyl-containing resin of Example 7a ofapplication S. N. l3'7,293, using 400 grams of it and 500 grams of thecarboxyl-containing resin in 300 grams xylene. The mixture was stirredand refluxed in a glass resin pot for 6 hours, in the presence of 3grams paratoluene sulfonic acid, the water of reaction being distilled.About 7 grams of water were so recovered. The product is asulfur-containing, acylation product, suitable for later use here.

Example 147b Santolite MS, a sulfonamide-aldehyde resin manufactured byMonsanto Chemical Company, St. Louis, wasoxyalkylated, as follows: UseSantolite MS, 500 grams; propylene oxide, 66 grams;

sodium methylate, 1 gram. Introduce the two reactants and the catalystinto the autoclave previously described and heat for 2.3 hours at atemperature of about 150 C., the pressure reaching 95 p. s. i. Nosolvent is required here, since the resin is soluble in propylene oxide.Thereafter, approximately 762 grams of ethylene oxide were introduced in12 portions, as follows: 44 grams in 4 hours, maximum temperature 150C.; 57 grams, same conditions; 62 grams, 3 hours, 150 C. maximum; 62grams, same conditions; 81 grams, same conditions; 71 grams plus 1 gramsodium methylate, 3.5 hours, 150 C. maximum; then six 65-gram portions,each requiring about 3 hours to add, with the maximum temperatureranging from about 145 C. to 150 C.

The oxyalkylated Santolite resin, which is a sulfur-containingacylation-susceptible material, was then reacted with thecarboxyl-containing phenol-aldehyde resin of Example 9a of applicationS. N. 137,293. In this reaction, 1230 grams of of the oxyalkylatedSantolite MS just prepared are mixed with 786 grams of thebutylphenol-salicylic acid-formaldehyde resin of Example 9a above, 1,000grams of xylene, and 20 grams of p-toluene sulfonic acid. The mixturewas stirred under reflux for 8 hours, water of reaction being distilled.The product is the desired acylated intermediate.

In the preparation of acylated intermediates 26 from sulfurorchlorine-containing acylationsusceptible reactants andcarboxyl-containing phenol-aldehyde resins we prefer that saidacylation-susceptible reactants have a molecular weight not exceeding25.000.

OXYALKYLATION We have prepared intermediates of the kind described aboveon a scale varying from a few hundred grams or less in the laboratory,to hundreds of pounds on a plant scale. The same applies in thepreparation of the oxyalkylated compounds with which this part of thespecification is com mediately follows refers to oxyethylation and it'is understood that oxypropylation can be handled conveniently in exactlythe same manner.

The oxyethylation procedure employed in the preparation of derivativesof the preceding intermediates has been uniformly the same, particularlyin light of the fact that a continuous operating procedure was employed.In this particular procedure the autoclave was aconventional autoclave,made of stainless steel and having a capacity of approximately onegallon, and a working pressure of 1,000 pounds gauge pressure. Theautoclave was equipped with the conventional devices and openings, suchas the variable stirrer operating at speeds from R. P. M. to 500R. P.M., thermometer well and thermocouple for mechanical thermometer:emptying outlet; pressure gauge, manual vent line; charge hole forinitial reactants; at least one connection for conducting the incomingalkylene oxide, such as ethylene oxide, to the bottom of the autoclave;along with suitable devices for both cooling and heating the autoclave,such as a cooling jacket 'and, preferably, coils in addition thereto,with the jacket so arranged that it is suitable for heating with steamor cooling with water, and further equipped with electrical heatingdevices. Such autoclaves are, of course, in essence small-scale replicasof the usual conventional autoclaves used in oxyalkylation procedures.

Continuous operation, or substantially continuous operation, is achievedby the use of a separate container to hold the alkylene oxide beingemployed, particularly ethylene oxide. The container consistsessentially of a laboratory bomb having a capacity of about one-halfgallon, or somewhat in excess thereof. This bomb was equipped, also,with an inlet for charging, and an outlet tube going to the bottom ofthe container so as to permit discharging of alkylene oxide in theliquid phase to the autoclave. Other con-- ventional equipment consists,of course, of the rupture disc, pressure gauge, sight feed glass,thermometer connection for nitrogen for pressuring bomb, etc. The bombwas placed on a scale during use and the connection between the bomb andthe autoclave were flexible stainless hose or tubing so that continuousweighings cou'd be made without breaking or making any connections. Thisalso applied to the nitrogen line, which was used to pressure the bombreservoir. To the extent that it was required, any other usualconventional procedure or addition which 27 provided greater safety wasused, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations becomeuniform in that the reaction temperature could be held within a fewdegrees of any selected point in this particular range. In the earlystages where the concentration of catalyst is high the temperature wasgenerally set for around 150 C. or thereabouts. Subsequentlytemperatures up to 170 C. or higher may be required. It will be noted byexamination of subsequent examples that this temperature range wassatisfactory. Inany case, where the reaction goes more slowly a hi hertemperature may be used, for instance, 165 C. to 180 C., and if need be185 C. to 190 C. Incidentally, oxypropylation takes place more slowlythan oxyethylation as a rule and for this reason we have used atemperature of approximately 160 C. to 165 C., as being particularlydesirable for initial oxypropylation, and have stayed within the rangeof 165 C. to 185 0., almost invariably during oxypropylation. Theethylene oxide was forced in by means of nitrogen pressure as rapidly asit was absorbed as indicated by the pressure gauge on the autoclave. Incase the reaction slowed .up the temperature was raised so as to speedup the reaction somewhat by use of extreme heat. If need be, coolingwater was employed to control the temperature.

As previously pointed out in the case of oxypropylation asdifferentiated from oxyethylation, there was a tendency for the reactionto slow up as the temperature dropped much below the selected point ofreaction, for instance, 170 C. In this instance the technique employedwas the same as before,,that is, either cooling water was cut down orsteam was employed, or the addition of propylene oxide speeded up, orelectric heat used in addition to the steam in order that the reactionproceeded at, or near, the selected temperatures to be maintained.

Inversely, if the reaction proceeded too fast regardless of theparticular alkylene oxide, the amount of reactant being added, such asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, are

dependent on the required number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventionaland, as far as we are aware, can be furnished by at least two firms whospecialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: (a) If prepared from'glycerol monochlorohydrin, this productshould be comparatively pure; (b) the glycide itself should be as pureas possible as the effect of impurities is diflicult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptl as introduced, i. e., that no excess ofglycide is allowed to accumulate; (d) all necessary precaution should betaken that glycide cannot polymerize per se; (e) due to the high boilingpoint of glycide one can readily employ a typical separable glass 'resinpot as described in the copending application of Melvin De Groote andBernhard Keiser, Serial No. 8,722, filed February 16, 1948, now Patent2.499.365 and offered for sale by numerous laboratory supply houses. Ifsuch arrangement is used to prepare laboratory scale duplications, thencare should be taken that the heating mantle can be removed rapidly soas to allow for cooling; or better still, through an added opening atthe top the glass resin pot or comparable vessel should be equipped witha stainless steel cooling coil so that the pot can be cooled morerapidly than by mere removal of mantle. If a stainless steel coil isintroduced it means that the conventional stirrer of the paddle type ischanged into the centrifugal type which causes the fluid or reactants tomix due to swirling action in the center of the pot. Still better, isthe use of a laboratory autoclave of the kind previously described, butin any event, when the initial amount of glycide is added to a suitablereactant, the speed of reaction'should be controlled by the usualfactors, such as (a) the addition of glycide; (b) the elimination ofexternal heat, and (c) use of cooling coil so there is no undue rise intemperature. All the foregoing is merely conventional but is includeddue to the hazard in handling glycide.

Example 10 The reaction vessel employed was a stainless steel autoclavewith the usual devices for heating, heat control, stirrer, inlet,outlet, etc., which is conventional in this type of apparatus. Thecapacity was approximately 3% liters. The stirrer operated at a speed ofapproximately 250 R. P. M. There were charged into the autoclave 257grams of the intermediate derivative, Example 94b above (in whichexample ethylene glycol and the amyl-phenol-salicylic-acid-formaldehyderesin of Example 7a of application S. N. 137,293 were reacted to producean ester which is the acylated product or intermediate employed in thepresent example), dissolved in 514 grams of solvent (xylene). 8 grams ofsodium methylate were added. The autoclave was sealed, swept withnitrogen gas, stirring started immediately and the temperature allowedto rise to 152.5 C. At this point addition of ethylene oxide wasstarted. It was added continuously at such speed that it was absorbed bythe reaction as rapidly as added. The amount of ethylene oxide added was254 grams. The time required to add the ethylene oxide was less than 10minutes, as a matter of fact, only about 5 minutes were required. Duringthis short reaction period the temperature rose rapidly to 180 C. Thetemperature was held at a maximum of 180 C., by using cooling waterthrough the coils when required, or otherwise applying heat when needed.The maximum pressure during this short reaction period was 215 pounds.The product at the end of this reaction was somewhat emulsitlable butnot clearly soluble.

The oxyethylation product produced as Just described was subjectedtofurther oxyethylation in the same manner, employing 326 grams of thesolventfree product of the first stage of oxyethylation, 326 grams ofxylene solvent, no additional catalyst, and 173 grams more of ethyleneoxide. In 5 minutes after introduction of the additional ethylene oxide,absorption thereof was substantially complete. The maximum temperaturein this second stage of oxyalkylation was C. and the maximum pressureobserved was p. s. i. The product was readily "water-soluble," i. e.,readily water-dispersible.

Referring back to Example 10 Just above, it

29 will be noted that a total of 427 grams of ethylene oxide wasemployed in the two stages of the reaction there conducted. When glycidewas substituted for ethylene oxide in the example, only 500 grams ofglycide were employed in spite of its molecular weight (about two-thirdsgreater than that of ethylene oxide). The glycide was charged into theupper reservoir vessel which had been flushed out previously withnitrogen and was the equivalent of a separatory funnel. of catalyst(sodium methylate) was reduced from 8 grams to grams. The glycide wasstarted slowly into the reaction mass in a dropwise stream. The reactionstarted to take place and the temperature rose approximately 12 to 18.

Cooling water was run through the coils so the temperature for theaddition of glycide was controlled within the range roughly of 110 C. to130 C. The addition was continuous within the The amount 10 limitationsand all the glycide was added in less than 4% hours. This reaction tookplace at atmospheric pressure with simply a small stream of nitrogenpassing into the autoclave at the very top and passing out through theopen condenser so as to avoid any entrance of air. The final product wasdistinctlywater-soluble.

The following table illustrates a number of other oxyalkylationderivatives of acylation or intermediate products described above allprepared in the manner outlined in Example 10 immediately preceding. Thetable identifies the products by example number, shows the amount ofintermediate product used, the amount of solvent, the amount ofcatalyst, the amount of alkylene oxide, the time required, the maximumtemperature andthe maximum pressure and indicates whether the product isemulsiflable or soluble in water.

Amt

Solvent Sod. Ratio Taken, EtO Temp. Max. Ex. Deriva- Gms. Present,Methylate Added, Time Max Pres" lbs. EtO to Solubility m water N o tiveN o. (solvent ms. Added, Gms (hrs.) 00 r s in Phenolic Free) (Xylene)Gms. De Hydroxyl lc. 2b 365 365 5 32 2 170 80 2 1 Not soluble. 2c 10 397365 32 1 165 80 4:1 Do. 3c- 2c 338 288 110 $6 165 140 13: 1 Watersoluble. 4a..-- 3b 244 126 5 92 2 170 150 2:1 Not soluble. 5c 42 248. 593. 5 1 170 130 4:1 D0. 6c. 56 232 68 145 $4 165 230 9. 9:1 Watersoluble. 7c. 6b 261. 5 261. 5 95 A 170 140 2: 1 N 06 soluble. 8c. 76254. 5 186. 5 1 165 110 4. 3:1v Do.

187. 5 137. 5 145 1 175 230 8:1 Water soluble. 11!) 316 316 115 16 170160 2:1 Insoluble. 312 228 60 K 170 80 4:1 Emulsitlable. 110 218 134 120$4 176 180 10. 1:1 Soluble. 121) 330 300 100 36 180 150 1. 95:1Insoluble. 1 3c 430 300 $6 185 160 4:1 Emulsiiiable. 140 286 160 165 M2185 200 10. 1:1 Soluble. 13b 332 111 85 H2 150 130 1. 8: 1 Insoluble.16c 326 86 50 H2 150 130 3. 2:1 Emulsifiable. 17c 278 64 300 it '180 25514:1 200 405 171 1 170 85 2:1 N 01; soluble. 19!: 528 171 165 1% 171 895: 1 Insoluble. 200 693 171 235 1 M 155 110 9:1 Soluble. 21c 405 155 M165 140 2: 1 Not soluble. 22c 535 155 160 $4 166 150 5:1 Insoluble. 23c695 155 225 94 170 170 9: 1 Soluble. 246 380 120 10 108 M 140 195 2: 1Not soluble. 25c 498 120 165 $4 155 156 5:1 Insoluble. 260 663 120 225$4 172 210 9:1 Soluble. 250 212 289 8 5'1 165 165 3:1 Insoluble. 280 219189 86 V4 160 150 6:1 Emulsiflable. 29c 183 113 80 $6 170 150 10. 9:1Soluble. 265 190 262 6 110 $6 165 170 2. 7:1 Insoluble. 310 199 174 9016 175 6. 1:1 Emulsiflable. 320 211 128 75 )4 170 120 10:1 Soluble. 275206 262 8 105 )4 160 170 2. 6 :1 Insoluble. 34c 210 178 95 M a 170 1406. 1 :1 Emulsiiiable. 350 184 108 70 M1 160 110 10.3:1 Soluble. 28b 175256 6 120 $4 175 170 3. 1641 Insoluble. 370 183 158 75 $4 165 6. 2: 1Emulsifiable. 386 179 110 70 $6 165 130 10. 4:1 Soluble. 295 265 291 8160 $4 170 185 3:1 Insoluble. 406 281 193 105 $6 185 150 6:1Emulsifiable. 41 c 267 133 105 1'6 170 150 10. 3:1 Soluble. 30b 236 2668 195 16 190 210 3. 12: 1 Emulsifiable. 43 281 174 H: 175 170 32:1Soluble. 34b 203 273 8 16 170 180 3 1 Emulsifiable. 45c 239 185 110 H:150 6. 32:1 Soluble. 350 237 252 8 V 155 1'6 175 180 3. 2:1Emulsifiable. 470 257 90 H2 165 120 6:1 Soluble. 36b 283 313 150 $6Insoluble. 490 309 224 110 Hz 170 Emulsifiable. 500 266 142 95 M: 170Semi-rub Water-Soluble. 37b 210 311 140 16 170 Insoluble. 520 225 324100 1 165 Emulslfiablo. 530 192 192 110 M2 170 Water-Soluble. 380 252253 210 $6 190 Insoluble. 55c 334 189 86 $6 170 Emulsifiable. 560 286129 109 H z 170 Water-Soluble. 395 250 269 150 y. Insoluble. 580 273 388115 16 170 Sem1-n1b., Emulsiflable. 59c 252 252 100 Hz 165Water-Soluble. 405 225 225 170 ,6 165 Insoluble. 610 256 366 110 M2 170Emulsifiable. 620 185 110 9i 2 170 Water-Soluble. 415 363 364 250 M2Insoluble.

64c 422 260 156 M2 180 Emulsiflable. 650 407 183 166 $6 180Water-Soluble. 42!) 229 335 110 92 165 Insoluble. 67: 236 234 105 M 170Semi-rub., Emulsiflable. 680 242 242 85 )6 160 Water-Soluble. 43b 249217 113 H 2 170 170 Insoluble. 70c 247 153 115 M a 170 170 D0. 716 20285 71 H: 170 140 Water-Soluble.

portions.

. However, went to rubber at 14:1. EtO added in two Example 1580 Thereaction vessel employed was a stainless steel autoclave equipped withthe usual devices for heating, heat control, stirrer, inlet, outlet,

etc., which are conventional for this type of apparatus. The capacitywas approximately 3.5 liters. The stirrer was operated at a speed ofapproximately 250 R. P. M. There was charged into this autoclave 216grams of the acylated intermediate, prepared in Example 106b above,dissolved in 392 grams of xylene as solvent. Then 8 grams of sodiummethylate catalyst were added. The autoclave was closed, then swept withnitrogen gas. Stirring was started and the by circulating cooling waterthrough the autoclave jacket or applying steam for heating, as required.The maximum pressure observed during the reaction was 220 p. s. i. Theoxyethylated 34 product so obtained was emulsifiable in water in thepresence of the xylene solvent.

Example 1590 The oxyethylated product of Example 158:: above (234 grams)diluted with 235 grams of xylene solvent, was reacted with an additional113 grams of ethylene oxide in the same manner as before, and withoutuse of additional catalyst. In 10 minutes absorption of this amount ofethylene oxide was complete, the temperature having risen to a maximumof 180 C. and the pressure to a maximum of 220 p. is. i. The resultingoxyethylated product was readily water-soluble (really, "waterdispersible) It was not further reacted with the alkylene oxide.

Various other oxyalkylation procedures were employed on the aeylatedintermediates previously prepared, all in the manner just set out above.These are shown in the following table. In it, the nature of theacylation product or intermediate, the amount of it employed, the amountof xylene employed as solvent, of sodium methylate catalyst employed, ifany, the amount of ethylene oxide used, the reaction time, maximumtemperature and pressure observed, and dispersibility of theoxyethylated product in water, are all set forth.

Max Max.

Ex. Prod. of Amt. Xylene Catalyst EtO Time,

No. Ex. No. (g.) (g.) (g.) (g.) Hrs. 8 6?" g i t; Water 1060 216 216 0.5 170 220 Emulsifiable. 1581: 234 113 0. 08 180 220 Soluble. 107D 180180 0. 16 180 220 Emulsiflable. 160:: 164 82 0. 08 170 150 Soluble. 108b198 212 0. 08 180 250 Emulsiflable. 162:: 212 108 0. 16 170 220 Soluble.

109!) 155 155 0. 25 180 200 Emulsiflable. 1646 161 t 0.16 160 150Soluble. 11012 175 190 0. 25 180 200 Emulsiflable. 1660 162 86 0. 16 160150 L- olu 9. 111b 196 210 0. 25 180 220 Emulslfiable. 1684: 204 107 0.16 160 150 Soluble. 1120 207 211 0. 25 180 220 Emulsifiable. l70c 220112 0. 16 160 150 Soluble. 1130 250 235 0. 16 170 220 Emulsiflable. 1726259 160 0. 08 180 200 Soluble. 1140 229 215 0. 16 175 220 Emulsiflable.174:: 288 180 0. 08 185 210 Soluble. 115!) 223 215 0. 16 180 210Emulsiflable. 1760 295 165 0. 08 185 190 Soluble. 116b 196 205 0. 08 180210 Emulsifiable. 1781: 0. 08 160 Soluble. 117b 194 200 0. 08 165 190Emulsiflable. 1800 215 140 0. 08 170 Soluble. 1180 202 200 0. 08 195Emulsifiable. 182:: 213 135 0. 08 150 140 Soluble. 119! 196 205 0. 08175 200 Emulsifiable. 184a 231 130 0. 08 160 160 Soluble. 12Gb 208 2080. 25 175 195 Emulsiflable. 1860 248 165 0. 08 185 Soluble. 1210 291 0.25 210 Emulsiflable 1880 336 175 0. 08 185 190 D0. 1890 333 60 0. 08 160110 Soluble. 1220 304 304 0. 25 190 230 Emulsifiable. 191c 333 175 0. 16210 Do. 192a 255 75 0. 16 160 150 Soluble. 1236 200 200 0. 33 175 190Eumulsifiable. 1946 226 145 0.16 175 u e. 1240 188 188 0. 08 165 210Emulsiflable. 1960 201 117 0. 08 180 170 Soluble. 1250 208 208 0. 25 175200 Emulsiflable. 1980 282 160 0. 16 175 185 Soluble. 1265 436 436 0. 33170 210 Emulsiflable. 2000 386 205 0. 08 160 205 Soluble. l27b 386 3860. 16 180 240 Emulsiflable. 2026 407 215 0. 08 170 200 D0. 2030: 326 2150. 33 170 200 Soluble. 1280 286 286 0. 08 175 200 Emulsifiable. 2056 366205 0. 08 185 210 Soluble. 1290 264 264 0. 16 165 200 Emulsifiable. 2070271 145 0. 08 175 Soluble. 1305 179 189 0. 16 170 200 Emulslflable. 2090204 120 0. 08 170 160 Soluble. 1311: 341 341 0. 08 190 220 Emulsifiaole.2111: 319 170 0.08 185 200 Do. 2120 253 135 0. 08 170 190 Soluble. 1320269 269 0. 25 180 190 Emulslfiable. 2146 306 165 0. 08 170 180 Soluble.1335 239 239 0.08 175 170 Emulsiiiable. 216a 275 155 0. 08 175 180Soluble. 1340 318 340 0.08 210 Emulsiflable. 2180 401 215 0. 08 195 210Soluble.

- 1356 299 305 0. 25 165 220 Emulsiflable.

1431: just above, from oxyethylated p-chlorophenol andamylphenol-salicylic acid-formaldehyde resin, 570 grams, was placed inthe oxyalkylation autoclave, along with 500 grams xylene and gramsstannic chloride. Ethylene oxide was introduced continuously until atotal of 1,300 grams had been absorbed. The maximum temperature notedduring oxyethylation was 170 C. The operation required '7 hours. Samplestaken from the autoclave showed progressively improvedwater-dispersibility, the final samples being quite water-dispersible.

Example 2390 170 C. A total of 1,300 grams of ethylene oxide was sointroduced in about Shows. The product exhibited increasingwater-dispersibility as oxyethylation level was raised, the finalproduct being quite water-dispersible.

Example 240c Use the acylated intermediate of Example 145b above, 735grams; xylene, 500 grams; stannic chloride, 7 grams. Place in theoxyalkylation autoclave, and introduce ethylene oxide continuously untila total of 440 grams has been absorbed. The time required is about 5hours. the maximum temperature, above 165 C. Then, introduce a total of116 grams propylene oxide into the mass, by disconnecting the ethyleneoxide supply and attaching the propylene oxide supply. Absorption wassomewhat slower, but was accomplished in 2 hours. Thereafter, introducean additional 110 grams ethylene oxide, as before. The time required wasabout 0.5 hour. The final product showed water-dispersibility.

Example 241::

The acylated intermediate of Example 14Gb above was used, 500 grams.Into the autoclave were also introduced 500 grams xylene and 5 gramsstannic chloride. Ethylene oxide, 440 grams, was then introduced incontinuous fashion, as above. Absorption was complete in 7 hours,maximum temperature being 170 C. The final product waswater-dispersible.

Max. Max. Ix. Prod. 01 Amt. X lene Catalyst EtO Time, No. Ex. No. (s-)t.) (a) (1.) Hrs. 213?" gfjf m 316 m m 0.08 1st 210 Soluble. 1:60 212 ma 272 0.08 210 Emullihble me 308 ans 0.0:; 175 m0 Soluble. m... 1370 so:M 10 ans 0.16 176 200 Emuldiiable m.-- m 368 368 an 0.CB 1K) 210 Do.me... 2261: 283 183 237 0.16 100 la) Soluble. an--- 13st :21 m 10 an0.10 m 210 Emumlieble 2270 424 411 no 0.0a no no Do. m as no m 0.14; 130Soluble. not 324 04a 10 m 0.10 no no Emuleifiable 281:-.- m as: m "'00.00 186 100 Soluble.

1400 an as m as 0.10 m :m Emuhifiable Ills.-- 232: 362 356 196 0A3 18)1M Soluble.

14m :27 664 10 am 0.10 195 210 Emullifiable 96-.. 234C 3W 3Q :00 04$ 1%220 Soluble.

mo 21: m a 21: 0.0a m 210 Emulsifiable an... m m 215 use 0.0:; no moSoluble.

Example 238a Example 2420 The acylated intermediate prepared in Example20 Use the acylated intermediate of Example 147!) above, 500 grams;xylene, 500 grams; and stannie chloride, 5 grams. Introduce this mixtureinto the autoclave and then feed ethylene oxide continuously until atotal or 550 grams have been absorbed. The time required was about 6hours. and the maximum temperature attained was C. The product waswater-dispersible.

In addition to ethylene oxide, propylene oxide, glycide, or mixtures ofthe two, or all three of these oxides, one can use also methyl glycideand butylene oxide. Butylene oxide, if employed at all, should be usedin combination with ethylene oxide, glycide or methyl glycide. The mostdesirable combination is, of course, one in which the oxyalkylatedderivative shows marked surface-activity, which can be readily detectedby an emulsification test as explained below.

The alpha-beta olefin oxides, employed to produce, from the acylatedintermediates, oxyalkylated derivatives which are distinctly hydrophilein nature, as shown by the fact that they are self-emulsifiable orselI-dispersible, miscible, or soluble in water, or have emulsifyingproperties, are characterized by the fact that they contain not over 8carbon atoms and are selected from the class consisting of ethyleneoxide, propylene oxide, butylene oxide, glycide, and methyl glycide.Glycide may, of course, be considered as a hydroxypropylene oxide andmethyl glycide as a hydroxybutylene oxide. In any event, all suchreactants contain the reactive ethylene oxide ring and may be bestconsidered as derivatives of, or substituted, ethylene oxides. Thesolubilizing effect of the oxide is directly proportional to thepercentage of oxygen present, or specifically, to the oxygencarbonratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3; and in methyl glycide, 1:2. In such compounds, the ratio is veryfavorable to the production of hydrophile or surface active properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly where the intermediate desired hydrophile product. The reverseprocedure may likewise be employed. Used alone, these two reagents mayin some cases fail to produce sufllciently hydrophile derivativesbecause of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is more effective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxy-propyleneoxide (glycide) is more effective than propylene oxide. Similarly,hydroxybutylene oxide (methyl glycide) is more effective than butyleneoxide. Since ethylene oxide is the cheapest alkylene oxide available andis reactive, its use is definitely advantageous, and especially in lightof its high oxygen content. Propylene oxide is less reactive thanethylene oxide, and butylene oxide is definitely less reactive thanpropylene oxide. On the other hand, glycide may react with almostexplosive violence and must be handled with extreme care, as previouslynoted.

As has been previously pointed out, the oxyalkylation of intermediatesof the kind from which the products used, in practicing the process ofthe present invention are prepared is advantageously catalyzed by thepresence of an alkali, except in certain cases, as where the product ischlorinated. in which case, to minimize dechlorination, a catalyst suchas stannic chloride (see Examples 2380-2420) is advantageously used.Useful a1- kaline catalysts include soaps, sodium acetate, sodiumhydroxide, sodium methylate, caustic potash, etc. The amount of alkalinecatalyst usually is between 0.2% to 2%. The temperature employed mayvary from room temperature to as high as 200 C. The reaction may beconducted with or without pressure, i. e., from zero pressure toapproximately 200 or even 300 pounds gauge pressure (pounds per squareinch). In a general way, the method employed is substantially the sameprocedure as used for oxyalkylation of other organic materials havingreactive phenolic groups.

It may be necessary to allow for the acidity of an intermediate indetermining the amount of alkaline catalyst to be added in itsoxyalkylation. For instance, if a nonvolatile strong acid such assulfuric acid is used to catalyze the resinification or intermediatereaction, presumably after being converted into a sulfonic acid, it maybe necessary and is usually advantageous to add an amount of alkaliequal stoichiometrically to such acidity, and include added alkali overand above this amount. as the alkaline catalyst.

It is advantageous to conduct the oxyethylation of the intermediate inpresence of an inert solvent such as xylene, cymene, decalin,ethyleneglycol diethylether, diethyleneglycol diethylether,

or the like, although with many products, the oxyalkylation proceedssatisfactorily without a solvent. Since xylene is cheap and may bepermitted to be present in the final product when used as a demulsifier,it is our preferenceto use xylene.

Considerable of what is said immediately hereinafter is concerned withthe ability to vary the hydrophile properties of the compounds used inthe process from minimum hydrophile properties to maximum hydrophileproperties. Even more remarkable, and equally difficult to explain, arethe versatility and utility of these compounds as one goes from minimumhydrophile property to ultimate maximum hydrophile property. Forinstance, minimum hydrophile property may be usually described roughlyas the point where two ethyleneoxy radicals or moderately in excessthereof are introduced per phenolic hydroxyl. Such minimum hydrophileproperty or sub-surface-activity or minimum surface-activity means thatthe product shows at least emulsifying properties or self-dispersion incold or even in warm distilled water (15 to 40 C.) in concentration of0.5% to 5.0%. These materials are generally more soluble in cold waterthan warm water; and may even be very insoluble in boiling water.Moderately high temperatures aid in reducing the viscosity of the soluteunder examination. Sometimes if ,one continues to shake a hot solution,even though cloudy or containing an insoluble phase, one finds thatsolution takes place to give a homogeneous phase as the m ture cools.Such self-dispersion tests are conduc ed in the absence of an insolublesolvent.

When the hydrophile-hydrophobe balance is above the indicated minimumbut insufllcient to give a sol as described immediately preceding, then,in that event hydrophile properties are indicated by the fact that onecan produce an emulsion by having present 10% to 50% of an inert solventsuch as xylene. All that one need to do is to have a xylene solutionwithin the range of 50 to parts by weight of oxyalkylated derivativesand 50 to 10 parts by weight of xylene, mix such solution with one, twoor three times its volume of distilled water, and shake vigorously so asto obtain an emulsion which may be of the oil-in-water type or thewater-in-oil type (usually the former) but, in any event, is due to thehydrophile-hydrophobe balance of the oxyalkylated derivative. We prefersimply to use the xylene-diluted derivatives, which are describedelsewhere, for this test rather than evaporate the solvent and employany more elaborate tests, if the solubility is not sufiicient to permitthe simple sol test in water previously noted.

If the product is not readily water-soluble it may be dissolved in ethylor methyl alcohol, ethyleneglycol diethylether, or diethyleneglycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to 50%, and then adding enoughof the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5% to 5.0% strength solution. If the product isself-dispersing (i. e., if the oxyalkylated product is a liquid or aliquid solution self-emulsifiable), such sol or dispersion is referredto as at least semi-stable in the sense that sols, emulsions, ordispersions prepared are relatively stable, if they remain at least forsome period of time, for instance 30 minutes to two hours, beforeshowing any marked separation. Such tests are conducted at roomtemperature (22 C.). Needless to say, a test can be made in presence ofan insoluble solvent such as 5% to 15% of xylene, as noted in previousexamples. If such mixture, i. e., containing a water-insoluble solvent,is at least semi-stable, obviously the solvent-free product would beeven more so. Surface-activity representing an advancedhydrophile-hydrophobe balance can also be determined by the use ofconventional measurements hereinafter described. One outstandingcharacteristic property indicating surface-activity in a material is theability to form a permanent foam in dilute aqueous solution, forexample, less than 0.5%, when in the higher oxyalkylated stage, and toform an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the 39 hydrophile properties of the flnalproduct. The principle involved in the manufacture of the hereincontemplated compounds for use as demulsifying agents or for other uses,is based on the conversion of a hydrophobe or non-hydra phile compoundor mixture of compounds into products which are distinctly hydrophile.at least to the extent that they have emulsifying properties or areself-emulsifying; that is, when shaken with water they produce stable orsemistable suspensions, or, in the presence of a waterinsoluble solvent,such as xylene, an emulsion. In demulsification, it is sometimespreferable to use a product having markedly enhanced hydrophileproperties over and above the initial stage of self-emulsiiiability,although we have found that with products of the type used herein, mostefficacious results are obtained with products which do not havehydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated acylated products give colloidal solutions orsols which show typical properties comparable to ordinary surfaceactiveagents. Such conventional surfaceactivity may be measured by determiningthe surface tension and the interfacial tension against paraiiin oil orthe like. At the initial and lower stages of oxyalkylation,surfaceactivity is not suitable determined in this same manner but onemay employ an emulsification test. Emulsions come into existence as arule through the presence of a surface-active emulsifying agent. Somesurface-active emulsifying agents such as mahogany soap may produce awater-in-oil emiusion or an oil-in-water emuldepending upon the ratio ofthe two phases, degree of agitation, concentration of emulsifying agent,etc.

'lhe same is true in regard to the oxyalkylated products hereinspecified, particularly in the lower stage of oxyalkylation, theso-called subsurface-active" stage. The surface-active properties arereadily demonstrated by producing a xylene-water emulsion. A suitableprocedure is as follows: The oxyalkylated product is dissolved in anequal weight of xylene. Such 50-50 solution is then mixed with 1-3volumes of water and shaken to produce an emulsion. The amount of xyleneis invariably sufficient to reduce even a tacky, resinous product to asolution which is readily water-dispersible. The emulsions so producedare usually xylene-inwater emulsions (oil -in-water type), particularlywhen the amount of distilled water used is at least slightly in excessof the volume of xylene solution and also if shaken vigorously. Attimes, particularly in the lowest stage of oxyalkylation', one mayobtain a water-in-xylene emulsion (water-in-oil type) which is apt toreverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 units per resin molecule. Such oxyalkylated resin, when dilutedwith an equal weight of xylene, will serve to illustrate the aboveemulsification test.

In a few instances, the product may not be sufficient soluble in xylenealone but may require the addition of some ethyleneglycol diethylether40 as described elsewhere. It is understood that such mixture, or anyother similar mixture, is considered the equivalent of xylene for thepurpose of test.

In manycases, there is no doubt as to the presence or absence ofhydrophile or surfaceactive' characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity), tests for emulsii'ying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebutylphenolformaldehyde resin derivative wherein 2 moles of ethyleneoxide have been introduced for each phenolic nucleus.

The presence of xylene or'an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixture and test such portion. In some cases,such xylenefree resultant may show initial or incipient hydrophileproperties,'whereas in presence of Xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientself-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor proportionsof common electrolytes as occur in oil field brines; I

Elsewhere, it is pointed out that an emulsiflcation test may be used todetermine ranges of surface-activity and that suchemulsiiication testsemploy a xylene solution. Stated another way, it is readily immaterialwhether a xylene solution produces a sci or whether it merely producesan emulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the effectivene of various alkylene oxides, andmost particularly of all ethylene oxide, to introduce hydrophilecharacter, it becomes obvious that there is a wide variation in theamount of alkylene oxide employed for producingproduc ts useful for thepractice of this invention. Another variation is the molecular size ofthe resin intermediate chain as is well understood.

The products of the present application are useful, not only asdemulsifying agents, but for other purposes where surface activematerials are of value, as, for example, producing emulsions,detergents, agricultural sprays, further reaction with chemicalcompounds reactive toward hydroxyl radicals, etc.

The process of breaking petroleum emulsions of the water in oil typeusing these new products is described and claimed in our applicationSerial No. 145,579, filed February 21, 1950, of which the presentapplication is a division. The intermediate acylation products, whichare onalkylated to

1. HYDROPHILE SYNTHETIC PRODUCTS, SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCT OF THE ACYLATION PRODUCT OBTAINED BY REACTING (A) A FUSIBLE CARBOXYL - CONTAINING, XYLENE-SOLUBLE, WATER-INSOLUBLE, LOW STAGE PHENOLALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A MIXTURE OF A DIFUNCTIONAL MONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOL AND SALICYLIC ACID ON THE ONE HAND, AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND ONE FUNCTIONAL GROUP REACTIVE TOWARD BOTH COMPONENTS OF THE MIXTURE ON THE OTHER HAND; THE AMOUNT OF SALICYLIC ACID EMPLOYED IN RELATION TO THE NONCARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE SALICYLIC ACID RADICAL PER RESIN MOLECULE AND THE AMOUNT OF NON-CARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE NONCARBOXYLATED PHENOL RADICAL PER RESIN MOLECULE; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO AND SAID PHENOL BEING OF THE FORMULA 